Acta Cryst. (2008). E64, o816 [ doi:10.1107/S1600536808008027 ]
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.
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.
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
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: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./sj2471fig1thm.gif)
| Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./sj2471fig2thm.gif)
| Fig. 2. The crystal packing of the title compound viewed along the c axis. Hydrogen bonds are drawn as dashed lines. |
| C8H5N5 | F000 = 352 |
| Mr = 171.17 | Dx = 1.424 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 6584 reflections |
| a = 4.9281 (10) Å | θ = 3.1–28.8º |
| b = 6.5420 (13) Å | µ = 0.10 mm−1 |
| c = 24.867 (5) Å | T = 293 (2) K |
| β = 95.27 (3)º | Prism, colorless |
| V = 798.3 (3) Å3 | 0.25 × 0.07 × 0.07 mm |
| Z = 4 |
| Rigaku SCXmini diffractometer | 1553 independent reflections |
| Radiation source: fine-focus sealed tube | 1167 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.061 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 26.0º |
| T = 293(2) K | θmin = 3.2º |
| ω scans | h = −6→6 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −8→8 |
| Tmin = 0.993, Tmax = 0.996 | l = −30→30 |
| 6844 measured reflections |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H 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 = 1.10 | Δρmax = 0.21 e Å−3 |
| 1553 reflections | Δρmin = −0.24 e Å−3 |
| 122 parameters | Extinction correction: SHELXL |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.044 (14) |
| Secondary atom site location: difference Fourier map |
| C8H5N5 | V = 798.3 (3) Å3 |
| Mr = 171.17 | Z = 4 |
| Monoclinic, P21/n | Mo Kα |
| a = 4.9281 (10) Å | µ = 0.10 mm−1 |
| b = 6.5420 (13) Å | T = 293 (2) K |
| c = 24.867 (5) Å | 0.25 × 0.07 × 0.07 mm |
| β = 95.27 (3)º |
| Rigaku SCXmini diffractometer | 1553 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1167 reflections with I > 2σ(I) |
| Tmin = 0.993, Tmax = 0.996 | Rint = 0.061 |
| 6844 measured reflections |
| R[F2 > 2σ(F2)] = 0.055 | 122 parameters |
| wR(F2) = 0.138 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.10 | Δρmax = 0.21 e Å−3 |
| 1553 reflections | Δρmin = −0.24 e Å−3 |
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. |
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.5249 (4) | 0.5054 (3) | 0.13602 (8) | 0.0345 (5) | |
| C2 | 0.6569 (4) | 0.5277 (3) | 0.08892 (8) | 0.0403 (5) | |
| C3 | 0.6021 (5) | 0.6960 (4) | 0.05536 (10) | 0.0548 (7) | |
| H3 | 0.6925 | 0.7116 | 0.0244 | 0.066* | |
| C4 | 0.4141 (5) | 0.8390 (4) | 0.06821 (11) | 0.0608 (7) | |
| H4 | 0.3762 | 0.9509 | 0.0457 | 0.073* | |
| C5 | 0.2821 (5) | 0.8174 (4) | 0.11410 (11) | 0.0539 (6) | |
| H5 | 0.1537 | 0.9140 | 0.1223 | 0.065* | |
| C6 | 0.3384 (4) | 0.6532 (3) | 0.14819 (9) | 0.0441 (6) | |
| H6 | 0.2504 | 0.6416 | 0.1796 | 0.053* | |
| C7 | 0.5736 (4) | 0.3299 (3) | 0.17202 (8) | 0.0323 (5) | |
| C8 | 0.8482 (5) | 0.3773 (4) | 0.07280 (9) | 0.0476 (6) | |
| N1 | 0.9990 (5) | 0.2612 (4) | 0.05847 (9) | 0.0701 (7) | |
| N2 | 0.3814 (3) | 0.2405 (3) | 0.19806 (7) | 0.0399 (5) | |
| N3 | 0.4920 (3) | 0.0893 (3) | 0.22916 (8) | 0.0480 (5) | |
| N4 | 0.7498 (3) | 0.0881 (3) | 0.22217 (7) | 0.0458 (5) | |
| N5 | 0.8068 (3) | 0.2363 (3) | 0.18650 (7) | 0.0380 (5) | |
| H2 | 0.195 (6) | 0.253 (4) | 0.1939 (10) | 0.072 (8)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0263 (10) | 0.0405 (11) | 0.0363 (11) | 0.0019 (9) | 0.0016 (8) | 0.0010 (9) |
| C2 | 0.0345 (12) | 0.0463 (12) | 0.0407 (12) | 0.0040 (10) | 0.0062 (9) | 0.0018 (10) |
| C3 | 0.0598 (16) | 0.0595 (15) | 0.0473 (14) | 0.0110 (12) | 0.0171 (12) | 0.0137 (12) |
| C4 | 0.0658 (17) | 0.0558 (15) | 0.0611 (17) | 0.0139 (13) | 0.0072 (14) | 0.0187 (13) |
| C5 | 0.0491 (14) | 0.0480 (14) | 0.0642 (16) | 0.0144 (11) | 0.0041 (12) | −0.0003 (12) |
| C6 | 0.0397 (12) | 0.0507 (13) | 0.0425 (13) | 0.0070 (10) | 0.0069 (10) | −0.0014 (10) |
| C7 | 0.0221 (9) | 0.0434 (11) | 0.0319 (11) | 0.0004 (8) | 0.0055 (8) | −0.0021 (9) |
| C8 | 0.0476 (13) | 0.0573 (15) | 0.0395 (13) | 0.0069 (12) | 0.0127 (10) | 0.0069 (11) |
| N1 | 0.0705 (15) | 0.0809 (15) | 0.0623 (15) | 0.0288 (13) | 0.0242 (12) | 0.0062 (12) |
| N2 | 0.0203 (9) | 0.0531 (11) | 0.0468 (11) | 0.0024 (8) | 0.0058 (8) | 0.0107 (8) |
| N3 | 0.0306 (9) | 0.0600 (12) | 0.0540 (12) | 0.0029 (9) | 0.0074 (8) | 0.0166 (10) |
| N4 | 0.0296 (9) | 0.0583 (12) | 0.0494 (11) | 0.0047 (8) | 0.0042 (8) | 0.0139 (9) |
| N5 | 0.0238 (8) | 0.0510 (10) | 0.0400 (10) | 0.0035 (8) | 0.0065 (7) | 0.0070 (8) |
| C1—C6 | 1.386 (3) | C5—H5 | 0.9300 |
| C1—C2 | 1.399 (3) | C6—H6 | 0.9300 |
| C1—C7 | 1.462 (3) | C7—N5 | 1.323 (2) |
| C2—C3 | 1.393 (3) | C7—N2 | 1.331 (2) |
| C2—C8 | 1.445 (3) | C8—N1 | 1.142 (3) |
| C3—C4 | 1.375 (3) | N2—N3 | 1.340 (2) |
| C3—H3 | 0.9300 | N2—H2 | 0.92 (3) |
| C4—C5 | 1.372 (3) | N3—N4 | 1.298 (2) |
| C4—H4 | 0.9300 | N4—N5 | 1.361 (2) |
| C5—C6 | 1.381 (3) | ||
| C6—C1—C2 | 118.61 (19) | C6—C5—H5 | 119.8 |
| C6—C1—C7 | 119.24 (18) | C5—C6—C1 | 120.5 (2) |
| C2—C1—C7 | 122.13 (17) | C5—C6—H6 | 119.7 |
| C3—C2—C1 | 120.31 (19) | C1—C6—H6 | 119.7 |
| C3—C2—C8 | 117.86 (19) | N5—C7—N2 | 107.65 (17) |
| C1—C2—C8 | 121.81 (19) | N5—C7—C1 | 128.31 (17) |
| C4—C3—C2 | 119.7 (2) | N2—C7—C1 | 123.99 (17) |
| C4—C3—H3 | 120.1 | N1—C8—C2 | 177.8 (2) |
| C2—C3—H3 | 120.1 | C7—N2—N3 | 109.61 (16) |
| C5—C4—C3 | 120.3 (2) | C7—N2—H2 | 130.9 (16) |
| C5—C4—H4 | 119.9 | N3—N2—H2 | 118.7 (16) |
| C3—C4—H4 | 119.9 | N4—N3—N2 | 106.16 (16) |
| C4—C5—C6 | 120.5 (2) | N3—N4—N5 | 110.25 (16) |
| C4—C5—H5 | 119.8 | C7—N5—N4 | 106.33 (15) |
| C6—C1—C2—C3 | 0.4 (3) | C6—C1—C7—N5 | −141.7 (2) |
| C7—C1—C2—C3 | 179.22 (19) | C2—C1—C7—N5 | 39.5 (3) |
| C6—C1—C2—C8 | −178.3 (2) | C6—C1—C7—N2 | 35.6 (3) |
| C7—C1—C2—C8 | 0.5 (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—C4 | 177.7 (2) | C1—C7—N2—N3 | −177.85 (18) |
| C2—C3—C4—C5 | 0.5 (4) | C7—N2—N3—N4 | 0.3 (2) |
| C3—C4—C5—C6 | 0.7 (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—C5 | 0.8 (3) | C1—C7—N5—N4 | 177.48 (19) |
| C7—C1—C6—C5 | −178.05 (19) | N3—N4—N5—C7 | 0.4 (2) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···N5i | 0.92 (3) | 1.91 (3) | 2.820 (2) | 172 (2) |
| N2—H2···N4i | 0.92 (3) | 2.60 (3) | 3.374 (2) | 142 (2) |
| Symmetry codes: (i) x−1, y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···N5i | 0.92 (3) | 1.91 (3) | 2.820 (2) | 172 (2) |
| N2—H2···N4i | 0.92 (3) | 2.60 (3) | 3.374 (2) | 142 (2) |
| Symmetry codes: (i) x−1, y, z. |
This project was supported by Jiangsu Education Department of China (No. 05KJB350031)
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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.