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Acta Crystallogr Sect E Struct Rep Online. 2008 May 1; 64(Pt 5): o816.
Published online 2008 April 10. doi:  10.1107/S1600536808008027
PMCID: PMC2961120

2-(1H-Tetra­zol-5-yl)benzonitrile

Abstract

The title compound, C8H5N5, was synthesized from phthalonitrile. The benzonitrile and tetra­zole rings are inclined at a dihedral angle of 37.14 (11)°. In the crystal structure, inter­molecular N—H(...)N hydrogen bonds link the tetra­zole rings of adjacent mol­ecules, forming chains along the a axis.

Related literature

For backgound to the chemisty of tetra­zoles, see: Bekhit et al. (2004 [triangle]); Aykut İkizler & Sancak (1992 [triangle], 1995 [triangle], 1998 [triangle]); Rajasekaran & Thampi (2004 [triangle]); Satyanarayana et al. (2006 [triangle]); Schmidt & Schieffer (2003 [triangle]); Upadhayaya et al. (2004 [triangle]); Wexler et al. (1996 [triangle]).

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Object name is e-64-0o816-scheme1.jpg

Experimental

Crystal data

  • C8H5N5
  • M r = 171.17
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o816-efi1.jpg
  • a = 4.9281 (10) Å
  • b = 6.5420 (13) Å
  • c = 24.867 (5) Å
  • β = 95.27 (3)°
  • V = 798.3 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 293 (2) K
  • 0.25 × 0.07 × 0.07 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.993, T max = 0.996
  • 6844 measured reflections
  • 1553 independent reflections
  • 1167 reflections with I > 2σ(I)
  • R int = 0.061

Refinement

  • R[F 2 > 2σ(F 2)] = 0.055
  • wR(F 2) = 0.138
  • S = 1.10
  • 1553 reflections
  • 122 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.24 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536808008027/sj2471sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808008027/sj2471Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This project was supported by Jiangsu Education Department of China (No. 05KJB350031)

supplementary crystallographic information

Comment

Nitriles are close relatives of azoles and hydrazones and are parent compounds for the preparation of various functional organic materials having triazole, imidazole or tetrazole rings (Aykut İkizler & Sancak, 1992, 1995, 1998). Tetrazoles find wide application in the synthesis of medicinal products such as antihypertensive agents (Wexler et al., 1996; Schmidt & Schieffer, 2003; Satyanarayana et al., 2006), resolvents (Bekhit et al., 2004), anaesthetics (Rajasekaran & Thampi, 2004) and antifungal agents (Upadhayaya et al., 2004). We report herein the crystal structure of the title compound, 2-(1H-tetrazol-5-yl)benzonitrile, Fig 1 with its crystal packing shown in Figure 2, Table 1.

Experimental

Phthalonitrile (1.28 g, 0.01 mol), sodium azide (0.975 g, 0.015 mol), ammonium chloride (0.605 g, 0.011 mol) and DMF (15 ml) were added in a flask and reacted at 120 °C with stirring for 24 h. A mass of white solid was collected after solvents removed. The crude product was recrystallized by slowly evaporating a mixed solution of ethanol and water (2:1) to yield colorless prism-like crystals, suitable for X-ray analysis.

Refinement

The H2 atom bound to N2 was located in a difference map and was refined freely. Other H atoms were placed in calculated positions, with C—H = 0.93 Å and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq

Figures

Fig. 1.
A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
The crystal packing of the title compound viewed along the c axis. Hydrogen bonds are drawn as dashed lines.

Crystal data

C8H5N5F000 = 352
Mr = 171.17Dx = 1.424 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 6584 reflections
a = 4.9281 (10) Åθ = 3.1–28.8º
b = 6.5420 (13) ŵ = 0.10 mm1
c = 24.867 (5) ÅT = 293 (2) K
β = 95.27 (3)ºPrism, colorless
V = 798.3 (3) Å30.25 × 0.07 × 0.07 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer1553 independent reflections
Radiation source: fine-focus sealed tube1167 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.061
Detector resolution: 13.6612 pixels mm-1θmax = 26.0º
T = 293(2) Kθmin = 3.2º
ω scansh = −6→6
Absorption correction: multi-scan(CrystalClear; Rigaku, 2005)k = −8→8
Tmin = 0.993, Tmax = 0.996l = −30→30
6844 measured reflections

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.055  w = 1/[σ2(Fo2) + (0.0619P)2 + 0.1285P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.138(Δ/σ)max < 0.001
S = 1.10Δρmax = 0.21 e Å3
1553 reflectionsΔρmin = −0.24 e Å3
122 parametersExtinction correction: SHELXL
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.044 (14)
Secondary atom site location: difference Fourier map

Special details

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)

xyzUiso*/Ueq
C10.5249 (4)0.5054 (3)0.13602 (8)0.0345 (5)
C20.6569 (4)0.5277 (3)0.08892 (8)0.0403 (5)
C30.6021 (5)0.6960 (4)0.05536 (10)0.0548 (7)
H30.69250.71160.02440.066*
C40.4141 (5)0.8390 (4)0.06821 (11)0.0608 (7)
H40.37620.95090.04570.073*
C50.2821 (5)0.8174 (4)0.11410 (11)0.0539 (6)
H50.15370.91400.12230.065*
C60.3384 (4)0.6532 (3)0.14819 (9)0.0441 (6)
H60.25040.64160.17960.053*
C70.5736 (4)0.3299 (3)0.17202 (8)0.0323 (5)
C80.8482 (5)0.3773 (4)0.07280 (9)0.0476 (6)
N10.9990 (5)0.2612 (4)0.05847 (9)0.0701 (7)
N20.3814 (3)0.2405 (3)0.19806 (7)0.0399 (5)
N30.4920 (3)0.0893 (3)0.22916 (8)0.0480 (5)
N40.7498 (3)0.0881 (3)0.22217 (7)0.0458 (5)
N50.8068 (3)0.2363 (3)0.18650 (7)0.0380 (5)
H20.195 (6)0.253 (4)0.1939 (10)0.072 (8)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0263 (10)0.0405 (11)0.0363 (11)0.0019 (9)0.0016 (8)0.0010 (9)
C20.0345 (12)0.0463 (12)0.0407 (12)0.0040 (10)0.0062 (9)0.0018 (10)
C30.0598 (16)0.0595 (15)0.0473 (14)0.0110 (12)0.0171 (12)0.0137 (12)
C40.0658 (17)0.0558 (15)0.0611 (17)0.0139 (13)0.0072 (14)0.0187 (13)
C50.0491 (14)0.0480 (14)0.0642 (16)0.0144 (11)0.0041 (12)−0.0003 (12)
C60.0397 (12)0.0507 (13)0.0425 (13)0.0070 (10)0.0069 (10)−0.0014 (10)
C70.0221 (9)0.0434 (11)0.0319 (11)0.0004 (8)0.0055 (8)−0.0021 (9)
C80.0476 (13)0.0573 (15)0.0395 (13)0.0069 (12)0.0127 (10)0.0069 (11)
N10.0705 (15)0.0809 (15)0.0623 (15)0.0288 (13)0.0242 (12)0.0062 (12)
N20.0203 (9)0.0531 (11)0.0468 (11)0.0024 (8)0.0058 (8)0.0107 (8)
N30.0306 (9)0.0600 (12)0.0540 (12)0.0029 (9)0.0074 (8)0.0166 (10)
N40.0296 (9)0.0583 (12)0.0494 (11)0.0047 (8)0.0042 (8)0.0139 (9)
N50.0238 (8)0.0510 (10)0.0400 (10)0.0035 (8)0.0065 (7)0.0070 (8)

Geometric parameters (Å, °)

C1—C61.386 (3)C5—H50.9300
C1—C21.399 (3)C6—H60.9300
C1—C71.462 (3)C7—N51.323 (2)
C2—C31.393 (3)C7—N21.331 (2)
C2—C81.445 (3)C8—N11.142 (3)
C3—C41.375 (3)N2—N31.340 (2)
C3—H30.9300N2—H20.92 (3)
C4—C51.372 (3)N3—N41.298 (2)
C4—H40.9300N4—N51.361 (2)
C5—C61.381 (3)
C6—C1—C2118.61 (19)C6—C5—H5119.8
C6—C1—C7119.24 (18)C5—C6—C1120.5 (2)
C2—C1—C7122.13 (17)C5—C6—H6119.7
C3—C2—C1120.31 (19)C1—C6—H6119.7
C3—C2—C8117.86 (19)N5—C7—N2107.65 (17)
C1—C2—C8121.81 (19)N5—C7—C1128.31 (17)
C4—C3—C2119.7 (2)N2—C7—C1123.99 (17)
C4—C3—H3120.1N1—C8—C2177.8 (2)
C2—C3—H3120.1C7—N2—N3109.61 (16)
C5—C4—C3120.3 (2)C7—N2—H2130.9 (16)
C5—C4—H4119.9N3—N2—H2118.7 (16)
C3—C4—H4119.9N4—N3—N2106.16 (16)
C4—C5—C6120.5 (2)N3—N4—N5110.25 (16)
C4—C5—H5119.8C7—N5—N4106.33 (15)
C6—C1—C2—C30.4 (3)C6—C1—C7—N5−141.7 (2)
C7—C1—C2—C3179.22 (19)C2—C1—C7—N539.5 (3)
C6—C1—C2—C8−178.3 (2)C6—C1—C7—N235.6 (3)
C7—C1—C2—C80.5 (3)C2—C1—C7—N2−143.2 (2)
C1—C2—C3—C4−1.1 (4)N5—C7—N2—N3−0.1 (2)
C8—C2—C3—C4177.7 (2)C1—C7—N2—N3−177.85 (18)
C2—C3—C4—C50.5 (4)C7—N2—N3—N40.3 (2)
C3—C4—C5—C60.7 (4)N2—N3—N4—N5−0.4 (2)
C4—C5—C6—C1−1.3 (4)N2—C7—N5—N4−0.2 (2)
C2—C1—C6—C50.8 (3)C1—C7—N5—N4177.48 (19)
C7—C1—C6—C5−178.05 (19)N3—N4—N5—C70.4 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···N5i0.92 (3)1.91 (3)2.820 (2)172 (2)
N2—H2···N4i0.92 (3)2.60 (3)3.374 (2)142 (2)

Symmetry codes: (i) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2471).

References

  • Aykut İkizler, A. & Sancak, K. (1992). Monatsh. Chem.123, 257–263.
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  • Aykut İkizler, A. & Sancak, K. (1998). Rev. Roum. Chim.43, 133–138.
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Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography