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ISSN: 2056-9890

5-p-Tolyl-1H-tetra­zole

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

(Received 31 July 2009; accepted 9 September 2009; online 12 September 2009)

The title compound, C8H8N4, possesses crystallographic mirror symmetry, with four C atoms lying on the reflecting plane, which bis­ects the phenyl and tetra­zole rings. It is composed of a planar r.m.s. deviation (0.0012 Å) tetra­zole ring which is nearly coplanar with the benzene ring, the dihedral angle being 2.67 (9)°. In the crystal, symmetry-related mol­ecules are linked by inter­molecular N—H⋯N hydrogen bonds. The mol­ecules stack along [100] with a ππ inter­action involving the phenyl and tetra­zole rings of adjacent mol­ecules [centroid–centroid distance = 3.5639 (15) Å]. The H atom of the N—H group is disordered over two sites of equal occupancy. The methyl H atoms were modelled as disordered over two sets of sites of equal occupancy rotated by 60° with respect to each other.

Related literature

For related manganese(II) complexes, see: Hu et al. (2007[Hu, B., Xu, X.-B., Li, Y.-X. & Ye, H.-Y. (2007). Acta Cryst. E63, m2698.]); Lü (2008[Lü, Y. (2008). Acta Cryst. E64, m1255.]). For applications of tetra­zoles in coordination chemistry, medicinal chemistry and materials science, see: Xiong et al. (2002[Xiong, R. G., Xue, X., Zhao, H., You, X. Z., Abrahams, B. F. & Xue, Z. L. (2002). Angew. Chem. Int. Ed. 41. 3800-3803.]); Xue et al. (2002[Xue, X., Wang, X. S., Wang, L. Z., Xiong, R. G., Abrahams, B. F., You, X. Z., Xue, Z. L. & Che, C.-M. (2002). Inorg. Chem. 41, 3800-3803.]); Wang et al. (2005[Wang, X. S., Tang, Y. Z., Huang, X. F., Qu, Z. R., Che, C. M., Chan, C. W. H. & Xiong, R. G. (2005). Inorg. Chem. 44, 5278-5285.]); Dunica et al. (1991[Dunica, J. V., Pierce, M. E. & Santella, J. B. III (1991). J. Org. Chem. 56, 2395-2400.]); Wittenberger et al. (1993[Wittenberger, S. J. & Donner, B. G. (1993). J. Org. Chem. 58, 4139-4141.]).

[Scheme 1]

Experimental

Crystal data
  • C8H8N4

  • Mr = 160.18

  • Orthorhombic, P b c m

  • a = 4.5370 (15) Å

  • b = 17.729 (5) Å

  • c = 9.778 (2) Å

  • V = 786.5 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 293 K

  • 0.20 × 0.20 × 0.20 mm

Data collection
  • Rigaku, SCXmini diffractometer

  • Absorption correction: multi-scan CrystalClear (Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.981, Tmax = 0.983

  • 7310 measured reflections

  • 946 independent reflections

  • 792 reflections with I > 2σ(I)

  • Rint = 0.040

Refinement
  • R[F2 > 2σ(F2)] = 0.048

  • wR(F2) = 0.115

  • S = 1.12

  • 946 reflections

  • 66 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.17 e Å−3

  • Δρmin = −0.16 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯N1i 0.87 (3) 1.94 (3) 2.806 (2) 171 (3)
Symmetry code: (i) [x, -y+{\script{1\over 2}}, -z+1].

Data collection: CrystalClear (Rigaku 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information


Comment top

Tetrazole-related molecules have attracted considerable attention due to their biological activities. The synthesis of new members of this family of ligands is an important direction in the development of modern coordination chemistry (Hu et al., 2007; Lü, 2008). Tetrazole compounds have a wide range of applications in coordination chemistry, medicinal chemistry and material science (Xiong, et al., 2002; Xue, et al., 2002; Wang, et al., 2005; Dunica, et al., 1991; Wittenberger, et al., 1993).

The title compound is a tetrazole ligand with a toluene substituent in position 5 (Fig. 1). In the solid state structure the molecule possesses crystallographic mirror symmetry. The mirror bisects the toluyl group and the tetrazole ring with atoms C1, C4, C7 and C8 lieing in the mirror. The bond lengths and angles have normal values. The interplanar angle between the phenyl ring [C1/C2/C3/C4/C2A/C3A] and the tetrazole ring [N1/N2/N1A/N2A/C7] mean-planes is 2.67 (9) °.

In the crystal symmetry related molecules are linked by intermolecular N—H···N hydrogen bonds (Table 1), forming chains propagating in the [010] direction (Fig. 2). There is a π···π interaction involving the tetrazole and phenyl rings of adjacent molecules with a centroid-to-centroid distance of 3.5639 (15) Å.

Related literature top

For related manganese(II) complexes, see: Hu et al. (2007); Lü (2008). For applications of tetrazoles in coordination chemistry, medicinal chemistry and materials science, see: Xiong et al. (2002); Xue et al. (2002); Wang et al. (2005); Dunica et al. (1991); Wittenberger et al. (1993).

Experimental top

4-methylbenzonitrile (1.17 g, 10 mmol) and ammonium chloride (0.53 g, 10 mmol) were dissolved in DMF (40 ml) in the presence of sodium azidein (0.98 g, 0.5 mmol) and refluxed for 24 h. After the mixture was cooled to rt and filtered. Most of the solvent was then removed under vacuum. Pale yellow crystals of the title compound, suitable for X-ray diffraction analysis, were obtained from the remaining solution on slow evaporation of the solvent.

Refinement top

All the H atoms could be located in the difference electron-density maps. Due to the mirror symmetry the NH H-atom, which is disorderd over N-atoms N1 and N1i [symmetry code (i) = x, y, -z+1/2], was freely refined with an occupancy of 0.5; distance N-H = 0.87 (3) Å. The C-bound H-atoms were included in idealized positions and treated as riding atoms: C-H = 0.93 - 0.96 Å, with Uiso(H) = 1.2Ueq(parent C-atom). The H-atoms on methyl C8 were modelled as disordered with two triplets of the H atoms with equal occupation (0.5:0.5) rotated by 60° to each other.

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); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with the displacement ellipsoids drawn at the 30% probability level. [Symmetry code: (A)= x, y, -z + 1/2].
[Figure 2] Fig. 2. Crystal packing diagram of the title compound, viewed along along the a axis (hydrogen bonds are shown as dashed lines, see Table 1 for details).
5-p-tolyl-1H-tetrazole top
Crystal data top
C8H8N4F(000) = 336
Mr = 160.18Dx = 1.353 Mg m3
Orthorhombic, PbcmMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2c 2bCell parameters from 1044 reflections
a = 4.5370 (15) Åθ = 3.0–27.4°
b = 17.729 (5) ŵ = 0.09 mm1
c = 9.778 (2) ÅT = 293 K
V = 786.5 (4) Å3Block, pale yellow
Z = 40.20 × 0.20 × 0.20 mm
Data collection top
Rigaku, SCXmini
diffractometer
946 independent reflections
Radiation source: fine-focus sealed tube792 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.040
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
CCD_Profile_fitting scansh = 55
Absorption correction: multi-scan
CrystalClear (Rigaku, 2005)
k = 2322
Tmin = 0.981, Tmax = 0.983l = 1212
7310 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.115 w = 1/[σ2(Fo2) + (0.0438P)2 + 0.1774P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max < 0.001
946 reflectionsΔρmax = 0.17 e Å3
66 parametersΔρmin = 0.16 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.023 (5)
Crystal data top
C8H8N4V = 786.5 (4) Å3
Mr = 160.18Z = 4
Orthorhombic, PbcmMo Kα radiation
a = 4.5370 (15) ŵ = 0.09 mm1
b = 17.729 (5) ÅT = 293 K
c = 9.778 (2) Å0.20 × 0.20 × 0.20 mm
Data collection top
Rigaku, SCXmini
diffractometer
946 independent reflections
Absorption correction: multi-scan
CrystalClear (Rigaku, 2005)
792 reflections with I > 2σ(I)
Tmin = 0.981, Tmax = 0.983Rint = 0.040
7310 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.12Δρmax = 0.17 e Å3
946 reflectionsΔρmin = 0.16 e Å3
66 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*/UeqOcc. (<1)
C10.2469 (4)0.17076 (11)0.25000.0386 (5)
C20.3511 (3)0.14064 (8)0.12792 (15)0.0478 (4)
H20.28950.16100.04510.057*
C30.5451 (4)0.08076 (9)0.12874 (17)0.0543 (5)
H30.61330.06160.04610.065*
C40.6408 (5)0.04856 (12)0.25000.0521 (6)
C70.0344 (4)0.23258 (11)0.25000.0363 (5)
C80.8408 (6)0.01930 (14)0.25000.0746 (8)
H8A0.88370.03360.34260.112*0.50
H8B1.02090.00710.20350.112*0.50
H8C0.74500.06040.20390.112*0.50
N10.0825 (3)0.26572 (7)0.35937 (12)0.0435 (4)
N20.2736 (3)0.31947 (7)0.31588 (13)0.0489 (4)
H10.064 (6)0.2534 (19)0.446 (3)0.045 (8)*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0394 (10)0.0431 (10)0.0333 (10)0.0074 (9)0.0000.000
C20.0540 (9)0.0525 (9)0.0369 (8)0.0014 (7)0.0021 (7)0.0017 (6)
C30.0544 (9)0.0552 (9)0.0532 (10)0.0016 (8)0.0081 (7)0.0105 (8)
C40.0428 (12)0.0430 (12)0.0705 (16)0.0079 (10)0.0000.000
C70.0415 (10)0.0411 (10)0.0262 (8)0.0109 (8)0.0000.000
C80.0601 (15)0.0542 (15)0.109 (2)0.0045 (13)0.0000.000
N10.0538 (7)0.0477 (7)0.0291 (6)0.0020 (6)0.0017 (5)0.0010 (5)
N20.0607 (8)0.0489 (7)0.0371 (6)0.0011 (6)0.0030 (6)0.0019 (5)
Geometric parameters (Å, º) top
C1—C21.3905 (18)C7—N1i1.3306 (17)
C1—C2i1.3905 (18)C7—N11.3306 (17)
C1—C71.460 (3)C8—H8A0.9600
C2—C31.379 (2)C8—H8B0.9600
C2—H20.9300C8—H8C0.9600
C3—C41.386 (2)N1—N21.3566 (17)
C3—H30.9300N1—H10.87 (3)
C4—C3i1.386 (2)N2—N2i1.288 (2)
C4—C81.507 (3)
C2—C1—C2i118.28 (19)N1i—C7—C1126.51 (9)
C2—C1—C7120.86 (10)N1—C7—C1126.51 (9)
C2i—C1—C7120.86 (10)C4—C8—H8A109.5
C3—C2—C1120.51 (15)C4—C8—H8B109.5
C3—C2—H2119.7H8A—C8—H8B109.5
C1—C2—H2119.7C4—C8—H8C109.5
C2—C3—C4121.47 (16)H8A—C8—H8C109.5
C2—C3—H3119.3H8B—C8—H8C109.5
C4—C3—H3119.3C7—N1—N2108.24 (12)
C3i—C4—C3117.7 (2)C7—N1—H1129 (2)
C3i—C4—C8121.17 (11)N2—N1—H1123 (2)
C3—C4—C8121.17 (11)N2i—N2—N1108.27 (7)
N1i—C7—N1106.98 (17)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N1ii0.87 (3)1.94 (3)2.806 (2)171 (3)
Symmetry code: (ii) x, y+1/2, z+1.

Experimental details

Crystal data
Chemical formulaC8H8N4
Mr160.18
Crystal system, space groupOrthorhombic, Pbcm
Temperature (K)293
a, b, c (Å)4.5370 (15), 17.729 (5), 9.778 (2)
V3)786.5 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.20 × 0.20 × 0.20
Data collection
DiffractometerRigaku, SCXmini
diffractometer
Absorption correctionMulti-scan
CrystalClear (Rigaku, 2005)
Tmin, Tmax0.981, 0.983
No. of measured, independent and
observed [I > 2σ(I)] reflections
7310, 946, 792
Rint0.040
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.115, 1.12
No. of reflections946
No. of parameters66
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.17, 0.16

Computer programs: CrystalClear (Rigaku 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N1i0.87 (3)1.94 (3)2.806 (2)171 (3)
Symmetry code: (i) x, y+1/2, z+1.
 

Acknowledgements

This work was supported by a start-up grant from Southeast University to ZRQ.

References

First citationDunica, J. V., Pierce, M. E. & Santella, J. B. III (1991). J. Org. Chem. 56, 2395–2400.
First citationFerguson, G. (1999). PRPKAPPA. University of Guelph, Canada.
First citationHu, B., Xu, X.-B., Li, Y.-X. & Ye, H.-Y. (2007). Acta Cryst. E63, m2698.  Web of Science CSD CrossRef IUCr Journals
First citationLü, Y. (2008). Acta Cryst. E64, m1255.  Web of Science CrossRef IUCr Journals
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationWang, X. S., Tang, Y. Z., Huang, X. F., Qu, Z. R., Che, C. M., Chan, C. W. H. & Xiong, R. G. (2005). Inorg. Chem. 44, 5278–5285.  Web of Science CSD CrossRef PubMed CAS
First citationWittenberger, S. J. & Donner, B. G. (1993). J. Org. Chem. 58, 4139–4141.  CrossRef CAS Web of Science
First citationXiong, R. G., Xue, X., Zhao, H., You, X. Z., Abrahams, B. F. & Xue, Z. L. (2002). Angew. Chem. Int. Ed. 41. 3800–3803.
First citationXue, X., Wang, X. S., Wang, L. Z., Xiong, R. G., Abrahams, B. F., You, X. Z., Xue, Z. L. & Che, C.-M. (2002). Inorg. Chem. 41, 3800–3803.  Web of Science CSD CrossRef

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