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access4-[(1H-Benzotriazol-1-yl)methyl]benzonitrile
aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: wxwang1109@yahoo.com
In the molecule of the title compound, C14H10N4, which was prepared by reaction of benzotriazole with 4-(bromomethyl)benzonitrile in alkaline solution, the dihedral angle between the benzotriazole and benzene ring systems is 69.03 (6)°.
Related literature
For the application of benzotriazole compounds in industry, see: Pillard et al. (2001![[Pillard, D. A., Cornell, J. S., Dufresne, D. L. & Hernandez, M. T. (2001). Water Res. 35, 557-560.]](../../../../../../logos/arrows/e_arr.gif "Pillard, D. A., Cornell, J. S., Dufresne, D. L. & Hernandez, M. T. (2001). Water Res. 35, 557-560.")
); Kopanska et al. (2004); Gruden et al. (2001). For the structure of a related compound, see: Selvanayagam et al. (2002).
![[Scheme 1]](rz2206scheme1.gif)
Experimental
Crystal data
|
Data collection: CrystalClear (Rigaku, 2005); cell 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); software used to prepare material for publication: SHELXTL.
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536808010969/rz2206sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536808010969/rz2206Isup2.hkl
A mixture of benzotriazole (0.01 mol) and KOH (0.56 g) in methanol (20 ml) was stirred for 10 min. 4-(Bromomethyl)benzonitrile (0.01 mol) was then added and the solution refluxed for 24 h. After completion of the reaction, the reaction mixture was evaporated under vacuum. Yellow crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of an ethanol solution after 3 days.
All H atoms were calculated geometrically and were refined using the riding-model approximation, with C—H =0.93-0.87 Å and with Uiso(H) = 1.2Ueq (C).
Data collection: CrystalClear (Rigaku, 2005); cell 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]](./rz2206fig1thm.gif) | Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. |
| C14H10N4 | F(000) = 488 |
| Mr = 234.26 | Dx = 1.304 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 2264 reflections |
| a = 8.1912 (13) Å | θ = 3.0–27.4° |
| b = 19.0520 (9) Å | µ = 0.08 mm−1 |
| c = 8.6610 (6) Å | T = 293 K |
| β = 118.039 (1)° | Block, yellow |
| V = 1193.0 (2) Å3 | 0.50 × 0.40 × 0.40 mm |
| Z = 4 |
| Rigaku Mercury2 diffractometer | 2715 independent reflections |
| Radiation source: fine-focus sealed tube | 1903 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.047 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
| CCD Profile fitting scans | h = −10→10 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −24→24 |
| Tmin = 0.960, Tmax = 0.969 | l = −11→11 |
| 11866 measured reflections |
| 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) = 0.182 | H-atom parameters constrained |
| S = 1.09 | w = 1/[σ2(Fo2) + (0.0763P)2 + 0.2728P] where P = (Fo2 + 2Fc2)/3 |
| 2715 reflections | (Δ/σ)max = 0.002 |
| 163 parameters | Δρmax = 0.34 e Å−3 |
| 0 restraints | Δρmin = −0.17 e Å−3 |
| C14H10N4 | V = 1193.0 (2) Å3 |
| Mr = 234.26 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 8.1912 (13) Å | µ = 0.08 mm−1 |
| b = 19.0520 (9) Å | T = 293 K |
| c = 8.6610 (6) Å | 0.50 × 0.40 × 0.40 mm |
| β = 118.039 (1)° |
| Rigaku Mercury2 diffractometer | 2715 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1903 reflections with I > 2σ(I) |
| Tmin = 0.960, Tmax = 0.969 | Rint = 0.047 |
| 11866 measured reflections |
| R[F2 > 2σ(F2)] = 0.067 | 0 restraints |
| wR(F2) = 0.182 | H-atom parameters constrained |
| S = 1.09 | Δρmax = 0.34 e Å−3 |
| 2715 reflections | Δρmin = −0.17 e Å−3 |
| 163 parameters |
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 | 0.7006 (4) | 0.10232 (14) | 0.9067 (4) | 0.0662 (7) | |
| H1A | 0.6891 | 0.1496 | 0.8769 | 0.079* | |
| C2 | 0.8443 (4) | 0.07658 (15) | 1.0621 (4) | 0.0714 (7) | |
| H2B | 0.9320 | 0.1081 | 1.1380 | 0.086* | |
| C3 | 0.8630 (4) | 0.00549 (15) | 1.1096 (4) | 0.0706 (7) | |
| C4 | 0.7387 (4) | −0.04391 (14) | 1.0033 (4) | 0.0674 (7) | |
| H4A | 0.7493 | −0.0911 | 1.0344 | 0.081* | |
| C5 | 0.5915 (3) | −0.01855 (12) | 0.8418 (3) | 0.0554 (6) | |
| C6 | 0.5771 (3) | 0.05233 (12) | 0.8006 (3) | 0.0546 (6) | |
| C7 | 0.3403 (4) | 0.11817 (13) | 0.5272 (3) | 0.0631 (6) | |
| H7A | 0.2790 | 0.1033 | 0.4058 | 0.076* | |
| H7B | 0.4372 | 0.1510 | 0.5420 | 0.076* | |
| C8 | 0.2010 (3) | 0.15545 (12) | 0.5681 (3) | 0.0513 (5) | |
| C9 | 0.2298 (3) | 0.22412 (12) | 0.6302 (3) | 0.0626 (6) | |
| H9A | 0.3379 | 0.2474 | 0.6504 | 0.075* | |
| C10 | 0.0989 (3) | 0.25833 (13) | 0.6624 (3) | 0.0616 (6) | |
| H10A | 0.1182 | 0.3044 | 0.7026 | 0.074* | |
| C11 | −0.0614 (3) | 0.22289 (11) | 0.6339 (3) | 0.0515 (5) | |
| C12 | −0.0901 (3) | 0.15394 (12) | 0.5744 (3) | 0.0583 (6) | |
| H12A | −0.1967 | 0.1302 | 0.5566 | 0.070* | |
| C13 | 0.0408 (3) | 0.12081 (12) | 0.5417 (3) | 0.0574 (6) | |
| H13A | 0.0212 | 0.0747 | 0.5015 | 0.069* | |
| C14 | −0.2037 (4) | 0.25735 (12) | 0.6617 (3) | 0.0621 (6) | |
| N1 | 0.4254 (3) | 0.05596 (10) | 0.6402 (3) | 0.0574 (5) | |
| N2 | 0.3499 (3) | −0.00893 (11) | 0.5862 (3) | 0.0684 (6) | |
| N3 | 0.4492 (3) | −0.05515 (11) | 0.7082 (3) | 0.0688 (6) | |
| N4 | −0.3207 (3) | 0.28251 (13) | 0.6795 (4) | 0.0841 (8) | |
| H3B | 0.9617 | −0.0085 | 1.2151 | 0.101* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0730 (16) | 0.0558 (14) | 0.0776 (18) | −0.0081 (12) | 0.0417 (14) | −0.0063 (12) |
| C2 | 0.0659 (16) | 0.0753 (18) | 0.0646 (17) | −0.0119 (13) | 0.0238 (13) | −0.0063 (13) |
| C3 | 0.0653 (16) | 0.0776 (18) | 0.0631 (16) | −0.0004 (13) | 0.0253 (13) | −0.0002 (13) |
| C4 | 0.0726 (17) | 0.0598 (15) | 0.0774 (18) | 0.0070 (12) | 0.0417 (15) | 0.0072 (13) |
| C5 | 0.0539 (13) | 0.0533 (13) | 0.0677 (15) | −0.0040 (10) | 0.0358 (12) | −0.0103 (11) |
| C6 | 0.0604 (14) | 0.0511 (12) | 0.0641 (14) | 0.0022 (10) | 0.0390 (12) | −0.0023 (10) |
| C7 | 0.0645 (15) | 0.0679 (15) | 0.0641 (15) | 0.0104 (12) | 0.0361 (12) | 0.0075 (12) |
| C8 | 0.0492 (12) | 0.0554 (13) | 0.0497 (12) | 0.0039 (9) | 0.0235 (10) | 0.0039 (10) |
| C9 | 0.0508 (13) | 0.0606 (15) | 0.0791 (17) | −0.0085 (10) | 0.0327 (12) | −0.0035 (12) |
| C10 | 0.0604 (14) | 0.0509 (13) | 0.0748 (16) | −0.0079 (11) | 0.0328 (12) | −0.0098 (11) |
| C11 | 0.0509 (12) | 0.0520 (12) | 0.0526 (13) | 0.0003 (9) | 0.0252 (10) | −0.0016 (10) |
| C12 | 0.0527 (13) | 0.0531 (13) | 0.0713 (15) | −0.0084 (10) | 0.0310 (12) | −0.0083 (11) |
| C13 | 0.0583 (14) | 0.0478 (12) | 0.0672 (15) | −0.0029 (10) | 0.0303 (12) | −0.0084 (10) |
| C14 | 0.0659 (15) | 0.0530 (13) | 0.0762 (16) | −0.0044 (11) | 0.0408 (13) | −0.0065 (12) |
| N1 | 0.0533 (11) | 0.0651 (12) | 0.0564 (12) | 0.0047 (9) | 0.0279 (9) | −0.0029 (9) |
| N2 | 0.0658 (13) | 0.0603 (13) | 0.0782 (15) | 0.0012 (10) | 0.0330 (11) | −0.0047 (11) |
| N3 | 0.0681 (13) | 0.0547 (12) | 0.0851 (15) | −0.0019 (10) | 0.0373 (12) | −0.0069 (11) |
| N4 | 0.0786 (16) | 0.0733 (15) | 0.119 (2) | −0.0010 (12) | 0.0622 (16) | −0.0153 (14) |
| C1—C6 | 1.379 (3) | C7—H7B | 0.9700 |
| C1—C2 | 1.396 (4) | C8—C13 | 1.388 (3) |
| C1—H1A | 0.9301 | C8—C9 | 1.392 (3) |
| C2—C3 | 1.403 (4) | C9—C10 | 1.391 (3) |
| C2—H2B | 0.9300 | C9—H9A | 0.9299 |
| C3—C4 | 1.374 (4) | C10—C11 | 1.391 (3) |
| C3—H3B | 0.9299 | C10—H10A | 0.9300 |
| C4—C5 | 1.435 (4) | C11—C12 | 1.390 (3) |
| C4—H4A | 0.9300 | C11—C14 | 1.453 (3) |
| C5—N3 | 1.384 (3) | C12—C13 | 1.383 (3) |
| C5—C6 | 1.387 (3) | C12—H12A | 0.9299 |
| C6—N1 | 1.362 (3) | C13—H13A | 0.9300 |
| C7—N1 | 1.486 (3) | C14—N4 | 1.145 (3) |
| C7—C8 | 1.521 (3) | N1—N2 | 1.363 (3) |
| C7—H7A | 0.9700 | N2—N3 | 1.321 (3) |
| C6—C1—C2 | 114.9 (2) | C13—C8—C9 | 119.1 (2) |
| C6—C1—H1A | 122.5 | C13—C8—C7 | 119.6 (2) |
| C2—C1—H1A | 122.5 | C9—C8—C7 | 121.3 (2) |
| C1—C2—C3 | 123.2 (2) | C10—C9—C8 | 120.7 (2) |
| C1—C2—H2B | 118.4 | C10—C9—H9A | 119.6 |
| C3—C2—H2B | 118.4 | C8—C9—H9A | 119.6 |
| C4—C3—C2 | 121.4 (2) | C11—C10—C9 | 119.3 (2) |
| C4—C3—H3B | 119.4 | C11—C10—H10A | 120.4 |
| C2—C3—H3B | 119.3 | C9—C10—H10A | 120.4 |
| C3—C4—C5 | 116.2 (2) | C12—C11—C10 | 120.4 (2) |
| C3—C4—H4A | 121.9 | C12—C11—C14 | 118.6 (2) |
| C5—C4—H4A | 121.9 | C10—C11—C14 | 121.0 (2) |
| N3—C5—C6 | 109.8 (2) | C13—C12—C11 | 119.7 (2) |
| N3—C5—C4 | 129.6 (2) | C13—C12—H12A | 120.2 |
| C6—C5—C4 | 120.6 (2) | C11—C12—H12A | 120.2 |
| N1—C6—C1 | 132.6 (2) | C12—C13—C8 | 120.8 (2) |
| N1—C6—C5 | 103.8 (2) | C12—C13—H13A | 119.6 |
| C1—C6—C5 | 123.6 (2) | C8—C13—H13A | 119.6 |
| N1—C7—C8 | 112.97 (18) | N4—C14—C11 | 177.3 (3) |
| N1—C7—H7A | 109.0 | C6—N1—N2 | 110.69 (19) |
| C8—C7—H7A | 109.0 | C6—N1—C7 | 129.3 (2) |
| N1—C7—H7B | 109.0 | N2—N1—C7 | 120.0 (2) |
| C8—C7—H7B | 109.0 | N3—N2—N1 | 108.7 (2) |
| H7A—C7—H7B | 107.8 | N2—N3—C5 | 107.0 (2) |
Experimental details
| Crystal data | |
| Chemical formula | C14H10N4 |
| Mr | 234.26 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 293 |
| a, b, c (Å) | 8.1912 (13), 19.0520 (9), 8.6610 (6) |
| β (°) | 118.039 (1) |
| V (Å3) | 1193.0 (2) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.08 |
| Crystal size (mm) | 0.50 × 0.40 × 0.40 |
| Data collection | |
| Diffractometer | Rigaku Mercury2 diffractometer |
| Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
| Tmin, Tmax | 0.960, 0.969 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 11866, 2715, 1903 |
| Rint | 0.047 |
| (sin θ/λ)max (Å−1) | 0.649 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.182, 1.09 |
| No. of reflections | 2715 |
| No. of parameters | 163 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.34, −0.17 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This work was supported by a Start-up Grant from SEU to Professor Ren-Gen Xiong.
References
Gruden, C. L., Dow, S. M. & Hernandez, M. T. (2001). Water Environ. Res. 73, 72–79. Web of Science CrossRef PubMed CAS Google Scholar
Kopanska, K., Najda, A., Zebrowska, J., Chomicz, L., Piekarczyk, J., Myjak, P. & Bretner, M. (2004). Bioorg. Med. Chem. 12, 2617–2624. Web of Science CrossRef PubMed CAS Google Scholar
Pillard, D. A., Cornell, J. S., Dufresne, D. L. & Hernandez, M. T. (2001). Water Res. 35, 557–560. Web of Science CrossRef PubMed CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Selvanayagam, S., Rajakannan, V., Velmurugan, D., Dhanasekaran, M., Rajakumar, P. & Moon, J.-K. (2002). Acta Cryst. E58, o1190–o1192. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Benzotriazole and its derivatives comprise an important class of corrosion inhibitors, typically used as trace additives in industrial chemical mixtures, such as coolants, cutting fluids and hydraulic fluid (Pillard et al., 2001). These derivatives are also used as inhibitors of Acanthamoeba castellanii (Kopanska et al., 2004) and are responsible for toxicity to bacteria (Gruden et al., 2001). In this paper the crystal structure of the title compound is reported.
In the title compound, bond lengths and angles observed in the benzotriazole ring system are comparable with those reported in other benzotriazole compounds (Selvanayagam et al., 2002). The dihedral angle between benzotriazole and benzene rings is 69.03 (6)°. The crystal structure is stabilized only by van der Waals contacts.