Acta Cryst. (2010). E66, o2732 [ doi:10.1107/S1600536810038948 ]
The title compound, C14H12N2, was synthesized by the reaction of 4-methyl-N-(2-nitrobenzyl)aniline with tin(II) chloride dihydrate in ethanol at 313 K. The indazole ring system is almost planar with a dihedral angle of 1.58 (10)° between the rings, whereas the plane of the attached p-tolyl substituent shows a dihedral angle of 46.26 (5)° with respect to the indazole core.
The title compound, (I), was prepared by the reaction of 4-methyl-N-(2-nitrobenzyl)aniline (3 mmol) and tin (II) chloride dihydrate (6 mmol) in ethanol (20 ml) at 313 K (yield: 40%). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an ethanolic solution. 1H NMR (DMSO-d6, δ): 2.39 (3H, s, CH3), 7.09–7.12 (1H, m, ArH), 7.29–7.33 (1H, m, ArH), 7.40 (2H, d, J = 8.4 Hz, ArH), 7.71 (1H, d, J = 8.8 Hz, ArH), 7.77 (1H, d, J = 8.8 Hz, ArH), 7.98 (2H, d, J = 8.4 Hz, ArH), 9.06 (1H, s, CH). 13C NMR (DMSO-d6, δ): 20.69, 117.56, 120.27, 121.01, 121.45, 122.13, 122.58, 126.77, 130.23, 137.53, 137.91, 148.98.
The C-bound H atoms were placed in calculated positions, with C—H = 0.93 or 0.96 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2–1.5(methyl) Ueq(C).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1999); 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]](./im2233fig1thm.gif)
| Fig. 1. The molecular structure of (I), showing 40% probability displacement ellipsoids and the atom-numbering scheme. |
![[Figure 2]](./im2233fig2thm.gif)
| Fig. 2. The crystal packing of (I). |
| C14H12N2 | F(000) = 440 |
| Mr = 208.26 | Dx = 1.273 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 1425 reflections |
| a = 12.539 (4) Å | θ = 2.8–24.4° |
| b = 6.029 (2) Å | µ = 0.08 mm−1 |
| c = 14.401 (5) Å | T = 298 K |
| β = 93.636 (5)° | Prism, colorless |
| V = 1086.4 (6) Å3 | 0.48 × 0.34 × 0.31 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 1915 independent reflections |
| Radiation source: fine-focus sealed tube | 1236 reflections with I > 2σ(I) |
| graphite | Rint = 0.039 |
| phi and ω scans | θmax = 25.0°, θmin = 2.2° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→14 |
| Tmin = 0.969, Tmax = 0.980 | k = −7→7 |
| 5372 measured reflections | l = −17→15 |
| 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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.140 | H-atom parameters constrained |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.0692P)2 + 0.1862P] where P = (Fo2 + 2Fc2)/3 |
| 1911 reflections | (Δ/σ)max < 0.001 |
| 145 parameters | Δρmax = 0.27 e Å−3 |
| 0 restraints | Δρmin = −0.26 e Å−3 |
| C14H12N2 | V = 1086.4 (6) Å3 |
| Mr = 208.26 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 12.539 (4) Å | µ = 0.08 mm−1 |
| b = 6.029 (2) Å | T = 298 K |
| c = 14.401 (5) Å | 0.48 × 0.34 × 0.31 mm |
| β = 93.636 (5)° |
| Bruker SMART CCD area-detector diffractometer | 1915 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1236 reflections with I > 2σ(I) |
| Tmin = 0.969, Tmax = 0.980 | Rint = 0.039 |
| 5372 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
| wR(F2) = 0.140 | Δρmax = 0.27 e Å−3 |
| S = 1.03 | Δρmin = −0.26 e Å−3 |
| 1911 reflections | Absolute structure: ? |
| 145 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | ||
| N1 | 0.57580 (13) | 0.0040 (3) | 0.35143 (12) | 0.0442 (5) | |
| N2 | 0.55544 (13) | 0.2100 (3) | 0.38504 (11) | 0.0420 (5) | |
| C1 | 0.64349 (16) | 0.3229 (4) | 0.41472 (14) | 0.0457 (6) | |
| H1 | 0.6458 | 0.4648 | 0.4401 | 0.055* | |
| C2 | 0.72979 (16) | 0.1879 (4) | 0.40029 (13) | 0.0433 (5) | |
| C3 | 0.84218 (17) | 0.2057 (4) | 0.41335 (16) | 0.0566 (7) | |
| H3 | 0.8738 | 0.3327 | 0.4393 | 0.068* | |
| C4 | 0.90270 (19) | 0.0330 (5) | 0.38714 (17) | 0.0631 (7) | |
| H4 | 0.9767 | 0.0421 | 0.3958 | 0.076* | |
| C5 | 0.85600 (18) | −0.1603 (4) | 0.34703 (16) | 0.0573 (7) | |
| H5 | 0.9002 | −0.2748 | 0.3295 | 0.069* | |
| C6 | 0.74854 (17) | −0.1839 (4) | 0.33324 (15) | 0.0490 (6) | |
| H6 | 0.7188 | −0.3122 | 0.3067 | 0.059* | |
| C7 | 0.68372 (16) | −0.0084 (3) | 0.36036 (13) | 0.0409 (5) | |
| C8 | 0.44707 (16) | 0.2872 (3) | 0.38157 (13) | 0.0417 (5) | |
| C9 | 0.36778 (16) | 0.1513 (4) | 0.41005 (14) | 0.0473 (6) | |
| H9 | 0.3846 | 0.0112 | 0.4338 | 0.057* | |
| C10 | 0.26299 (17) | 0.2226 (4) | 0.40340 (15) | 0.0516 (6) | |
| H10 | 0.2097 | 0.1297 | 0.4231 | 0.062* | |
| C11 | 0.23572 (17) | 0.4304 (4) | 0.36780 (15) | 0.0486 (6) | |
| C12 | 0.31752 (18) | 0.5648 (4) | 0.34099 (16) | 0.0538 (6) | |
| H12 | 0.3012 | 0.7054 | 0.3177 | 0.065* | |
| C13 | 0.42283 (18) | 0.4963 (4) | 0.34777 (15) | 0.0508 (6) | |
| H13 | 0.4767 | 0.5901 | 0.3298 | 0.061* | |
| C14 | 0.12148 (18) | 0.5069 (5) | 0.35741 (19) | 0.0705 (8) | |
| H14A | 0.0757 | 0.3925 | 0.3788 | 0.106* | |
| H14B | 0.1025 | 0.5382 | 0.2931 | 0.106* | |
| H14C | 0.1133 | 0.6386 | 0.3937 | 0.106* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0509 (12) | 0.0386 (11) | 0.0432 (10) | −0.0059 (8) | 0.0047 (8) | −0.0025 (8) |
| N2 | 0.0471 (10) | 0.0377 (10) | 0.0415 (10) | −0.0048 (8) | 0.0052 (8) | −0.0015 (8) |
| C1 | 0.0542 (13) | 0.0396 (12) | 0.0435 (12) | −0.0105 (11) | 0.0031 (10) | −0.0045 (10) |
| C2 | 0.0475 (13) | 0.0466 (13) | 0.0358 (11) | −0.0073 (10) | 0.0036 (9) | 0.0012 (10) |
| C3 | 0.0516 (14) | 0.0626 (16) | 0.0550 (15) | −0.0127 (12) | −0.0006 (11) | −0.0055 (12) |
| C4 | 0.0455 (14) | 0.0786 (19) | 0.0649 (16) | −0.0015 (13) | 0.0008 (11) | 0.0010 (14) |
| C5 | 0.0574 (16) | 0.0582 (16) | 0.0569 (15) | 0.0101 (12) | 0.0085 (11) | 0.0021 (12) |
| C6 | 0.0571 (14) | 0.0443 (13) | 0.0462 (13) | −0.0015 (11) | 0.0089 (10) | 0.0016 (10) |
| C7 | 0.0474 (13) | 0.0419 (13) | 0.0338 (11) | −0.0041 (10) | 0.0061 (9) | 0.0037 (9) |
| C8 | 0.0481 (12) | 0.0409 (13) | 0.0360 (11) | −0.0024 (10) | 0.0034 (9) | −0.0015 (9) |
| C9 | 0.0538 (14) | 0.0410 (13) | 0.0471 (13) | −0.0047 (11) | 0.0024 (10) | 0.0072 (10) |
| C10 | 0.0494 (14) | 0.0526 (15) | 0.0530 (14) | −0.0080 (11) | 0.0044 (10) | 0.0026 (11) |
| C11 | 0.0513 (13) | 0.0533 (15) | 0.0408 (12) | 0.0021 (11) | −0.0006 (10) | −0.0063 (11) |
| C12 | 0.0639 (16) | 0.0453 (14) | 0.0516 (14) | 0.0050 (12) | −0.0002 (11) | 0.0034 (11) |
| C13 | 0.0569 (15) | 0.0437 (14) | 0.0523 (14) | −0.0078 (11) | 0.0064 (10) | 0.0051 (11) |
| C14 | 0.0573 (16) | 0.082 (2) | 0.0707 (17) | 0.0118 (14) | −0.0054 (12) | −0.0070 (15) |
| N1—C7 | 1.353 (2) | C6—H6 | 0.9300 |
| N1—N2 | 1.362 (2) | C8—C9 | 1.371 (3) |
| N2—C1 | 1.344 (2) | C8—C13 | 1.378 (3) |
| N2—C8 | 1.434 (3) | C9—C10 | 1.380 (3) |
| C1—C2 | 1.380 (3) | C9—H9 | 0.9300 |
| C1—H1 | 0.9300 | C10—C11 | 1.388 (3) |
| C2—C3 | 1.414 (3) | C10—H10 | 0.9300 |
| C2—C7 | 1.422 (3) | C11—C12 | 1.381 (3) |
| C3—C4 | 1.356 (3) | C11—C14 | 1.503 (3) |
| C3—H3 | 0.9300 | C12—C13 | 1.381 (3) |
| C4—C5 | 1.411 (3) | C12—H12 | 0.9300 |
| C4—H4 | 0.9300 | C13—H13 | 0.9300 |
| C5—C6 | 1.357 (3) | C14—H14A | 0.9600 |
| C5—H5 | 0.9300 | C14—H14B | 0.9600 |
| C6—C7 | 1.405 (3) | C14—H14C | 0.9600 |
| C7—N1—N2 | 103.03 (16) | C9—C8—C13 | 120.3 (2) |
| C1—N2—N1 | 113.95 (17) | C9—C8—N2 | 119.91 (19) |
| C1—N2—C8 | 127.16 (19) | C13—C8—N2 | 119.78 (19) |
| N1—N2—C8 | 118.82 (16) | C8—C9—C10 | 119.9 (2) |
| N2—C1—C2 | 106.85 (19) | C8—C9—H9 | 120.1 |
| N2—C1—H1 | 126.6 | C10—C9—H9 | 120.1 |
| C2—C1—H1 | 126.6 | C9—C10—C11 | 121.2 (2) |
| C1—C2—C3 | 136.0 (2) | C9—C10—H10 | 119.4 |
| C1—C2—C7 | 104.43 (17) | C11—C10—H10 | 119.4 |
| C3—C2—C7 | 119.5 (2) | C12—C11—C10 | 117.6 (2) |
| C4—C3—C2 | 118.4 (2) | C12—C11—C14 | 120.8 (2) |
| C4—C3—H3 | 120.8 | C10—C11—C14 | 121.6 (2) |
| C2—C3—H3 | 120.8 | C11—C12—C13 | 121.9 (2) |
| C3—C4—C5 | 121.5 (2) | C11—C12—H12 | 119.0 |
| C3—C4—H4 | 119.2 | C13—C12—H12 | 119.0 |
| C5—C4—H4 | 119.2 | C8—C13—C12 | 119.1 (2) |
| C6—C5—C4 | 121.9 (2) | C8—C13—H13 | 120.4 |
| C6—C5—H5 | 119.0 | C12—C13—H13 | 120.4 |
| C4—C5—H5 | 119.0 | C11—C14—H14A | 109.5 |
| C5—C6—C7 | 117.8 (2) | C11—C14—H14B | 109.5 |
| C5—C6—H6 | 121.1 | H14A—C14—H14B | 109.5 |
| C7—C6—H6 | 121.1 | C11—C14—H14C | 109.5 |
| N1—C7—C6 | 127.45 (19) | H14A—C14—H14C | 109.5 |
| N1—C7—C2 | 111.74 (18) | H14B—C14—H14C | 109.5 |
| C6—C7—C2 | 120.80 (19) |
Bistochi, G. A., De Meo, G., Pedini, M., Ricci, A., Brouilhet, H., Bucherie, S., Rabaud, M. & Jacquignon, P. (1981). Farm. Ed. Sci. 36, 315–333.
Bruker (1998). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Cerecetto, H., Gerpe, A., Gonzalez, M., Aran, V. J. & de Ocarizi, C. O. (2005). Mini Rev. Med. Chem. 5, 869–878.
Corsi, G., Palazzo, G., Germani, C., Barcellona, P. S. & Silvestrini, B. (1976). J. Med. Chem. 19, 778–783.
Keppler, B. K. & Hartmann, M. (1994). Met. Based Drugs, 1, 145–149.
Picciola, G., Ravenna, F., Carenimi, G., Gentili, P. & Riva, M. (1981). Farm. Ed. Sci. 36, 1037–1056.
Rodgers, J. D., Johnson, B. L., Wang, H., Greenberg, R. A., Erickson, V. S., Klabe, R. M., Cordova, B. C., Rayner, M. M., Lam, G. N. & Chang, C. H. (1996). Bioorg. Med. Chem. Lett. 6, 2919–2924.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Stadlbauer, W. (2002). Science of Synthesis, Vol. 12. Stuttgart: Thieme.
Sun, J. H., Teleha, C. A., Yan, J. S., Rodgers, J. D. & Nugiel, D. A. (1997). J. Org. Chem. 62, 5627–5629.
Ykeda, Y., Takano, N., Matsushita, H., Shiraki, Y., Koide, T., Nagashima, R., Fujimura, Y., Shindo, M., Suzuki, S. & Iwasaki, T. (1979). Arzneim. Forsch. 29, 511–520.
Indazole is well known as an aza analogue of indole, and a number of indazole derivatives have powerful pharmacological activities including anti-inflammatory (Bistochi et al., 1981; Picciola et al., 1981), antitumor (Keppler & Hartmann, 1994), anti-HIV (Sun et al., 1997; Rodgers et al., 1996), antidepressant (Ykeda et al., 1979), contraceptive activities (Corsi et al., 1976) as well as anti-aggregatory, and vasorelaxant activity by NO release (Cerecetto et al., 2005). Different approaches to the synthesis of 2-substituted indazoles have been reported (Stadlbauer, 2002). However, many of these still suffer from drawbacks as unsatisfactory yields, long reaction time and high temperature. Therefore, the development of more efficient methods for preparation of this kind of compounds is still an active research area.
We report here the crystal structure of the title compound, (I), which was synthesized by the reaction of 4-methyl-N-(2-nitrobenzyl)aniline with tin (II) chloride dihydrate using ethanol as solvent at 313 K.
In (I), the pyrazole ring (C1/C2/C7/N1/N2) is a new formed ring. The dihedral angle between the C1/C2/C7/N1/N2 plane and the C2/C3/C4/C5/C6/C7 plane is 1.58 (10)°, so the indazole ring shows an almost perfectly planar conformation. The dihedral angle between the C2/C3/C4/C5/C6/C7 plane and the C8/C9/C10/C11/C12/C13 of the p-tolyl substituent plane is 46.26 (5)°.