1-(4-Methyl­phen­yl)-1H-1,2,3,4-tetra­zole

Baek, K.; Gayathri, D.; Gupta, V.K.; Kant, R.; Jeong, Y.T.

doi:10.1107/S1600536812000797

organic compounds

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Volume 68| Part 2| February 2012| Page o394

doi:10.1107/S1600536812000797

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1-(4-Methylphenyl)-1H-1,2,3,4-tetrazole

Kwan Baek,^a D. Gayathri,^b Vivek K. Gupta,^c Rajni Kant ^c and Yeon Tae Jeong ^a ^*

^aDepartment of Image Science and Engineering, Pukyong National University, Busan 608 739, Republic of Korea, ^bDepartment of Physics, Dr. M.G.R Educational and Research Institute, Dr. M.G.R University, Maduravoyal, Chennai 600 095, India, and ^cX-ray Crystallography Laboratory, Post Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India
^*Correspondence e-mail: ytjeong@pknu.ac.kr

(Received 5 January 2012; accepted 9 January 2012; online 14 January 2012)

In the title compound, C₈H₈N₄, the dihedral angle between the tetrazole and benzene rings is 21.6 (1)°. An intermolecular C—H⋯π interaction is observed.

Related literature

For background to and applications of tetrazole derivatives, see: Singh et al. (1980 ); Brown (1967 ); Ostrovskii et al. (1999 ). For the synthesis, see: Aridoss & Laali (2011 ). For related structures, see: Matsunaga et al. (1999 ); Lyakhov et al. (2000 ).

Experimental

Crystal data

C₈H₈N₄
M_r = 160.18
Monoclinic, P 2₁ /n
a = 9.8352 (13) Å
b = 5.7244 (6) Å
c = 14.4190 (19) Å
β = 96.285 (12)°
V = 806.92 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.1 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.762, T_max = 1.000
14618 measured reflections
1419 independent reflections
936 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.211
S = 1.05
1419 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯Cgⁱ	0.93	2.89	3.630 (3)	138
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812000797/is5047sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812000797/is5047Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812000797/is5047Isup3.cml

checkCIF report

Comment top

Tetrazoles are an important functional group with wide range of applications (Aridoss & Laali, 2011). They function as ligands in coordination chemistry, in medicinal chemistry as a metabolically stable surrogate for a carboxylic acid group (Singh et al., 1980) and in materials science applications including propellants (Brown, 1967) and explosives (Ostrovskii et al., 1999).

Bond lengths and bond angles are comparable with the similar crystal structures (Matsunaga et al., 1999; Lyakhov et al., 2000). The tetrazole and benzene rings are planar with maximum deviations of 0.006 (2) and 0.011 (2) Å (r.m.s. deviations of the rings being 0.005 and 0.008 Å), respectively. The two rings are not coplanar with the dihedral angle being 21.6 (1)°. Methyl carbon atom lies 0.014 (5) Å from the plane of the phenyl ring. Bond distances C1—N1 [1.304 (4) Å] and N2—N3 [1.289 (4) Å] indicate the consistence of the formation of double bonds.

Related literature top

For background to and applications of tetrazole derivatives, see: Singh et al. (1980); Brown (1967); Ostrovskii et al. (1999). For the synthesis, see: Aridoss & Laali (2011). For related structures, see: Matsunaga et al. (1999); Lyakhov et al. (2000).

Experimental top

The title compound was synthesized from the known procedure reported elsewhere (Aridoss & Laali, 2011). Fine white diffraction quality crystals were obtained from the slow evaporation of its solution in ethanol.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids.

1-(4-Methylphenyl)-1H-1,2,3,4-tetrazole top

Crystal data top

C₈H₈N₄	F(000) = 336
M_r = 160.18	D_x = 1.319 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3527 reflections
a = 9.8352 (13) Å	θ = 3.6–29.2°
b = 5.7244 (6) Å	µ = 0.09 mm⁻¹
c = 14.4190 (19) Å	T = 293 K
β = 96.285 (12)°	Plate, white
V = 806.92 (17) Å³	0.3 × 0.2 × 0.1 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	1419 independent reflections
Radiation source: fine-focus sealed tube	936 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
Detector resolution: 16.1049 pixels mm^-1	θ_max = 25.0°, θ_min = 3.8°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −6→6
T_min = 0.762, T_max = 1.000	l = −17→17
14618 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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.211	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.1133P)² + 0.1542P] where P = (F_o² + 2F_c²)/3
1419 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₈H₈N₄	V = 806.92 (17) Å³
M_r = 160.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.8352 (13) Å	µ = 0.09 mm⁻¹
b = 5.7244 (6) Å	T = 293 K
c = 14.4190 (19) Å	0.3 × 0.2 × 0.1 mm
β = 96.285 (12)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	1419 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	936 reflections with I > 2σ(I)
T_min = 0.762, T_max = 1.000	R_int = 0.054
14618 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.211	H-atom parameters constrained
S = 1.05	Δρ_max = 0.21 e Å⁻³
1419 reflections	Δρ_min = −0.25 e Å⁻³
110 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
C1	0.7153 (3)	0.0846 (5)	0.8500 (2)	0.0726 (9)
H1	0.7271	−0.0729	0.8372	0.087*
C2	0.4656 (3)	0.0810 (4)	0.87347 (17)	0.0540 (7)
C3	0.3730 (3)	0.1934 (5)	0.92335 (18)	0.0635 (8)
H3	0.3959	0.3336	0.9537	0.076*
C4	0.2465 (3)	0.0950 (5)	0.9274 (2)	0.0672 (9)
H4	0.1838	0.1718	0.9605	0.081*
C5	0.2090 (3)	−0.1143 (5)	0.88414 (19)	0.0622 (8)
C6	0.3039 (3)	−0.2219 (5)	0.8337 (2)	0.0634 (8)
H6	0.2811	−0.3625	0.8036	0.076*
C7	0.4315 (3)	−0.1253 (4)	0.82696 (18)	0.0607 (8)
H7	0.4932	−0.1980	0.7918	0.073*
C8	0.0709 (3)	−0.2228 (6)	0.8897 (2)	0.0850 (10)
H8A	0.0534	−0.2328	0.9538	0.127*
H8B	0.0692	−0.3767	0.8631	0.127*
H8C	0.0017	−0.1283	0.8558	0.127*
N1	0.8114 (3)	0.2424 (5)	0.85255 (19)	0.0841 (9)
N2	0.7502 (3)	0.4443 (5)	0.8748 (2)	0.0874 (9)
N3	0.6234 (3)	0.4089 (4)	0.8848 (2)	0.0826 (9)
N4	0.5985 (2)	0.1809 (4)	0.86824 (14)	0.0580 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.077 (2)	0.0625 (18)	0.081 (2)	0.0000 (16)	0.0255 (17)	−0.0042 (15)
C2	0.0584 (16)	0.0504 (15)	0.0528 (15)	0.0089 (11)	0.0041 (12)	0.0054 (11)
C3	0.079 (2)	0.0557 (16)	0.0568 (17)	0.0051 (14)	0.0129 (14)	−0.0082 (13)
C4	0.071 (2)	0.0697 (19)	0.0636 (18)	0.0125 (15)	0.0181 (15)	−0.0055 (14)
C5	0.0616 (18)	0.0644 (17)	0.0609 (17)	0.0079 (13)	0.0075 (14)	0.0067 (13)
C6	0.0678 (18)	0.0531 (16)	0.0686 (18)	0.0045 (13)	0.0046 (14)	−0.0049 (13)
C7	0.0661 (19)	0.0524 (15)	0.0635 (18)	0.0138 (13)	0.0073 (14)	−0.0052 (12)
C8	0.066 (2)	0.101 (3)	0.088 (2)	−0.0003 (17)	0.0104 (17)	−0.0046 (19)
N1	0.0828 (19)	0.086 (2)	0.087 (2)	−0.0101 (15)	0.0223 (15)	0.0017 (14)
N2	0.085 (2)	0.0721 (18)	0.106 (2)	−0.0069 (15)	0.0121 (16)	0.0022 (15)
N3	0.082 (2)	0.0569 (16)	0.108 (2)	0.0002 (13)	0.0060 (16)	−0.0030 (13)
N4	0.0649 (15)	0.0519 (13)	0.0568 (14)	0.0047 (11)	0.0048 (11)	0.0029 (10)

Geometric parameters (Å, º) top

C1—N1	1.304 (4)	C5—C8	1.504 (4)
C1—N4	1.326 (3)	C6—C7	1.385 (4)
C1—H1	0.9300	C6—H6	0.9300
C2—C3	1.380 (4)	C7—H7	0.9300
C2—C7	1.381 (4)	C8—H8A	0.9600
C2—N4	1.436 (3)	C8—H8B	0.9600
C3—C4	1.373 (4)	C8—H8C	0.9600
C3—H3	0.9300	N1—N2	1.357 (4)
C4—C5	1.382 (4)	N2—N3	1.288 (4)
C4—H4	0.9300	N3—N4	1.345 (3)
C5—C6	1.389 (4)

N1—C1—N4	110.3 (3)	C5—C6—H6	119.1
N1—C1—H1	124.8	C2—C7—C6	118.8 (3)
N4—C1—H1	124.8	C2—C7—H7	120.6
C3—C2—C7	120.8 (3)	C6—C7—H7	120.6
C3—C2—N4	119.9 (2)	C5—C8—H8A	109.5
C7—C2—N4	119.2 (2)	C5—C8—H8B	109.5
C4—C3—C2	119.0 (3)	H8A—C8—H8B	109.5
C4—C3—H3	120.5	C5—C8—H8C	109.5
C2—C3—H3	120.5	H8A—C8—H8C	109.5
C3—C4—C5	122.3 (2)	H8B—C8—H8C	109.5
C3—C4—H4	118.8	C1—N1—N2	105.0 (3)
C5—C4—H4	118.8	N3—N2—N1	110.6 (2)
C4—C5—C6	117.4 (3)	N2—N3—N4	107.0 (2)
C4—C5—C8	122.1 (3)	C1—N4—N3	107.1 (2)
C6—C5—C8	120.5 (3)	C1—N4—C2	131.2 (2)
C7—C6—C5	121.7 (3)	N3—N4—C2	121.7 (2)
C7—C6—H6	119.1

C7—C2—C3—C4	1.0 (4)	C1—N1—N2—N3	−0.1 (4)
N4—C2—C3—C4	180.0 (2)	N1—N2—N3—N4	−0.6 (4)
C2—C3—C4—C5	0.7 (4)	N1—C1—N4—N3	−1.2 (3)
C3—C4—C5—C6	−1.4 (4)	N1—C1—N4—C2	180.0 (3)
C3—C4—C5—C8	179.3 (3)	N2—N3—N4—C1	1.1 (3)
C4—C5—C6—C7	0.3 (4)	N2—N3—N4—C2	−180.0 (2)
C8—C5—C6—C7	179.7 (3)	C3—C2—N4—C1	157.9 (3)
C3—C2—C7—C6	−2.0 (4)	C7—C2—N4—C1	−23.2 (4)
N4—C2—C7—C6	179.0 (2)	C3—C2—N4—N3	−20.7 (4)
C5—C6—C7—C2	1.3 (4)	C7—C2—N4—N3	158.2 (2)
N4—C1—N1—N2	0.9 (3)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C2–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Cgⁱ	0.93	2.89	3.630 (3)	138

Symmetry code: (i) −x+1/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₈H₈N₄
M_r	160.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.8352 (13), 5.7244 (6), 14.4190 (19)
β (°)	96.285 (12)
V (Å³)	806.92 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.3 × 0.2 × 0.1

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.762, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	14618, 1419, 936
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.211, 1.05
No. of reflections	1419
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.25

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C2–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Cgⁱ	0.93	2.89	3.630 (3)	138

Symmetry code: (i) −x+1/2, y−1/2, −z+3/2.

Acknowledgements

KB and YTJ acknowledge the support provided by the second stage of the BK21 Program. RK thanks the DST, New Delhi, India, for the X-ray data collection facility.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o394

doi:10.1107/S1600536812000797

Open

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