Acta Cryst. (2008). E64, o2449 [ doi:10.1107/S1600536808038944 ]
In the molecular structure of the title compound, C16H13N3, the cyclohexa-1,3-diene ring displays a screw-boat conformation and the pyridine ring is twisted by a dihedral angle of 29.13 (9)° with respect to the pyrazole ring. Molecules are linked into a supramolecular structure by N-H
N hydrogen bonding.
A solution of 3,4-dihydronaphthalen-1(2H)-one (1.46 g, 0.01 mol) was added to a stirred solution of hydrazine (0.05 g, 0.01 mol) in dry tetrahydrofuran (50 ml) at 273 K for 3 h. Then n-butyllithium (0.02 mol) was added at a fast dropwise rate during a 5 min period at 273 K. The solution was stirred at 273 K for an additional 30 min, then methyl isonicotinate (1.37 g, 0.01 mol) dissolved in 40 ml of THF was added to the dilithiated intermediate, and the solution was stirred for 1 h at 273 K. Finally, 20 ml of 3 M hydrochloric acid was added, and the two phase mixture was well stirred and heated under reflux for 45 min. The mixture was then neutralized with solid sodium bicarbonate, and the layers were separated. The aqueous layer was extracted with ether. The organic fractions were combined, evaporated, the crude product was dissolved in methanol (60 ml). The solution was filtered and the filtrate was set aside for three weeks to obtain colorless single crystals of the title compound.
H atoms were placed in calculated positions with C—H = 0.93 or 0.97 Å, N—H = 0.86 Å, and refined in riding mode with Uiso(H) = 1.2Ueq(C,N).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./xu2463fig1thm.gif)
| Fig. 1. The molecular structure of (I) showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. |
| C16H13N3 | F(000) = 1040 |
| Mr = 247.29 | Dx = 1.310 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 2217 reflections |
| a = 15.306 (2) Å | θ = 2.2–25.0° |
| b = 8.8368 (13) Å | µ = 0.08 mm−1 |
| c = 18.543 (3) Å | T = 293 K |
| V = 2508.1 (6) Å3 | Block, colorless |
| Z = 8 | 0.22 × 0.19 × 0.18 mm |
| Bruker SMART CCD area-detector diffractometer | 1978 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.036 |
| graphite | θmax = 25.0°, θmin = 2.2° |
| φ and ω scans | h = −18→17 |
| 24926 measured reflections | k = −10→9 |
| 2217 independent reflections | l = −22→22 |
| 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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.130 | H-atom parameters constrained |
| S = 1.08 | w = 1/[σ2(Fo2) + (0.0626P)2 + 0.7587P] where P = (Fo2 + 2Fc2)/3 |
| 2217 reflections | (Δ/σ)max < 0.001 |
| 172 parameters | Δρmax = 0.44 e Å−3 |
| 0 restraints | Δρmin = −0.25 e Å−3 |
| C16H13N3 | V = 2508.1 (6) Å3 |
| Mr = 247.29 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 15.306 (2) Å | µ = 0.08 mm−1 |
| b = 8.8368 (13) Å | T = 293 K |
| c = 18.543 (3) Å | 0.22 × 0.19 × 0.18 mm |
| Bruker SMART CCD area-detector diffractometer | 1978 reflections with I > 2σ(I) |
| 24926 measured reflections | Rint = 0.036 |
| 2217 independent reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
| wR(F2) = 0.130 | Δρmax = 0.44 e Å−3 |
| S = 1.08 | Δρmin = −0.25 e Å−3 |
| 2217 reflections | Absolute structure: ? |
| 172 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 | ||
| N2 | 0.37603 (9) | 0.33266 (16) | 0.11204 (7) | 0.0442 (4) | |
| H2 | 0.3299 | 0.3882 | 0.1124 | 0.053* | |
| N1 | 0.43088 (9) | 0.32191 (17) | 0.05503 (8) | 0.0458 (4) | |
| C2 | 0.65724 (12) | 0.2397 (2) | −0.07332 (10) | 0.0563 (5) | |
| H2A | 0.6747 | 0.3078 | −0.1087 | 0.068* | |
| C11 | 0.41088 (14) | 0.1591 (2) | 0.29215 (10) | 0.0567 (5) | |
| C5 | 0.56409 (10) | 0.18489 (19) | 0.02662 (9) | 0.0436 (4) | |
| C7 | 0.40188 (10) | 0.24622 (18) | 0.16853 (9) | 0.0415 (4) | |
| C12 | 0.36103 (11) | 0.2337 (2) | 0.23932 (9) | 0.0466 (4) | |
| C8 | 0.47774 (11) | 0.17516 (19) | 0.14790 (9) | 0.0438 (4) | |
| C6 | 0.49343 (10) | 0.22560 (19) | 0.07685 (9) | 0.0425 (4) | |
| C4 | 0.60463 (11) | 0.0446 (2) | 0.02934 (10) | 0.0484 (4) | |
| H4 | 0.5881 | −0.0261 | 0.0639 | 0.058* | |
| C9 | 0.52238 (13) | 0.0675 (2) | 0.19845 (11) | 0.0631 (5) | |
| H9A | 0.5018 | −0.0346 | 0.1895 | 0.076* | |
| H9B | 0.5849 | 0.0696 | 0.1899 | 0.076* | |
| C1 | 0.66954 (11) | 0.0109 (2) | −0.01959 (10) | 0.0534 (5) | |
| H1 | 0.6958 | −0.0838 | −0.0165 | 0.064* | |
| N3 | 0.69715 (9) | 0.10469 (18) | −0.07098 (8) | 0.0534 (4) | |
| C3 | 0.59220 (12) | 0.2840 (2) | −0.02683 (10) | 0.0528 (5) | |
| H3 | 0.5672 | 0.3795 | −0.0311 | 0.063* | |
| C13 | 0.27959 (13) | 0.2938 (2) | 0.25682 (11) | 0.0614 (5) | |
| H13 | 0.2468 | 0.3434 | 0.2219 | 0.074* | |
| C14 | 0.37630 (18) | 0.1460 (3) | 0.36132 (11) | 0.0726 (6) | |
| H14 | 0.4082 | 0.0962 | 0.3968 | 0.087* | |
| C15 | 0.29537 (18) | 0.2057 (3) | 0.37810 (12) | 0.0771 (7) | |
| H15 | 0.2733 | 0.1959 | 0.4246 | 0.092* | |
| C16 | 0.24751 (16) | 0.2795 (3) | 0.32620 (12) | 0.0761 (7) | |
| H16 | 0.1932 | 0.3200 | 0.3378 | 0.091* | |
| C10 | 0.50413 (16) | 0.1100 (3) | 0.27516 (12) | 0.0759 (7) | |
| H10A | 0.5432 | 0.1918 | 0.2884 | 0.091* | |
| H10B | 0.5183 | 0.0240 | 0.3055 | 0.091* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N2 | 0.0354 (7) | 0.0488 (8) | 0.0484 (8) | 0.0074 (6) | −0.0015 (6) | 0.0005 (6) |
| N1 | 0.0395 (8) | 0.0497 (8) | 0.0480 (8) | 0.0035 (6) | −0.0009 (6) | 0.0016 (6) |
| C2 | 0.0498 (11) | 0.0611 (12) | 0.0579 (11) | −0.0071 (9) | 0.0052 (8) | 0.0048 (9) |
| C11 | 0.0704 (12) | 0.0498 (11) | 0.0499 (10) | −0.0028 (9) | −0.0010 (9) | 0.0031 (8) |
| C5 | 0.0331 (8) | 0.0480 (9) | 0.0496 (9) | −0.0036 (7) | −0.0023 (7) | −0.0032 (7) |
| C7 | 0.0375 (9) | 0.0422 (9) | 0.0447 (9) | −0.0016 (7) | −0.0033 (7) | −0.0008 (7) |
| C12 | 0.0474 (10) | 0.0449 (9) | 0.0474 (9) | −0.0077 (8) | 0.0013 (7) | −0.0040 (7) |
| C8 | 0.0379 (9) | 0.0430 (9) | 0.0504 (10) | 0.0011 (7) | −0.0024 (7) | 0.0020 (7) |
| C6 | 0.0361 (8) | 0.0416 (9) | 0.0498 (9) | −0.0019 (7) | −0.0022 (7) | 0.0007 (7) |
| C4 | 0.0412 (9) | 0.0455 (10) | 0.0585 (10) | −0.0024 (7) | 0.0045 (8) | 0.0002 (8) |
| C9 | 0.0590 (12) | 0.0645 (12) | 0.0658 (12) | 0.0145 (10) | −0.0004 (9) | 0.0158 (10) |
| C1 | 0.0428 (10) | 0.0493 (10) | 0.0681 (12) | −0.0001 (8) | 0.0046 (8) | −0.0068 (9) |
| N3 | 0.0396 (8) | 0.0601 (10) | 0.0605 (9) | −0.0063 (7) | 0.0053 (7) | −0.0069 (7) |
| C3 | 0.0455 (10) | 0.0520 (11) | 0.0610 (11) | 0.0020 (8) | 0.0051 (8) | 0.0058 (9) |
| C13 | 0.0494 (11) | 0.0756 (13) | 0.0592 (11) | −0.0032 (10) | 0.0058 (9) | −0.0080 (10) |
| C14 | 0.0972 (18) | 0.0692 (14) | 0.0515 (11) | −0.0096 (13) | 0.0013 (11) | 0.0068 (10) |
| C15 | 0.0888 (17) | 0.0870 (16) | 0.0554 (12) | −0.0268 (14) | 0.0208 (12) | −0.0080 (11) |
| C16 | 0.0628 (13) | 0.0966 (17) | 0.0689 (13) | −0.0122 (12) | 0.0210 (11) | −0.0184 (13) |
| C10 | 0.0849 (14) | 0.0828 (16) | 0.0600 (12) | 0.0256 (12) | −0.0095 (11) | 0.0120 (11) |
| N2—N1 | 1.353 (2) | C4—C1 | 1.378 (2) |
| N2—C7 | 1.356 (2) | C4—H4 | 0.9300 |
| N2—H2 | 0.8600 | C9—C10 | 1.497 (3) |
| N1—C6 | 1.343 (2) | C9—H9A | 0.9700 |
| C2—N3 | 1.341 (3) | C9—H9B | 0.9700 |
| C2—C3 | 1.374 (3) | C1—N3 | 1.332 (2) |
| C2—H2A | 0.9300 | C1—H1 | 0.9300 |
| C11—C14 | 1.393 (3) | C3—H3 | 0.9300 |
| C11—C12 | 1.406 (3) | C13—C16 | 1.383 (3) |
| C11—C10 | 1.525 (3) | C13—H13 | 0.9300 |
| C5—C4 | 1.387 (2) | C14—C15 | 1.382 (4) |
| C5—C3 | 1.391 (2) | C14—H14 | 0.9300 |
| C5—C6 | 1.472 (2) | C15—C16 | 1.374 (4) |
| C7—C8 | 1.374 (2) | C15—H15 | 0.9300 |
| C7—C12 | 1.458 (2) | C16—H16 | 0.9300 |
| C12—C13 | 1.393 (3) | C10—H10A | 0.9700 |
| C8—C6 | 1.412 (2) | C10—H10B | 0.9700 |
| C8—C9 | 1.500 (2) | ||
| N1—N2—C7 | 112.52 (13) | C8—C9—H9A | 109.6 |
| N1—N2—H2 | 123.7 | C10—C9—H9B | 109.6 |
| C7—N2—H2 | 123.7 | C8—C9—H9B | 109.6 |
| C6—N1—N2 | 104.56 (13) | H9A—C9—H9B | 108.1 |
| N3—C2—C3 | 124.28 (18) | N3—C1—C4 | 124.42 (18) |
| N3—C2—H2A | 117.9 | N3—C1—H1 | 117.8 |
| C3—C2—H2A | 117.9 | C4—C1—H1 | 117.8 |
| C14—C11—C12 | 118.3 (2) | C1—N3—C2 | 115.61 (16) |
| C14—C11—C10 | 121.50 (19) | C2—C3—C5 | 119.47 (18) |
| C12—C11—C10 | 119.84 (17) | C2—C3—H3 | 120.3 |
| C4—C5—C3 | 116.76 (16) | C5—C3—H3 | 120.3 |
| C4—C5—C6 | 121.60 (16) | C16—C13—C12 | 120.0 (2) |
| C3—C5—C6 | 121.63 (16) | C16—C13—H13 | 120.0 |
| N2—C7—C8 | 106.80 (14) | C12—C13—H13 | 120.0 |
| N2—C7—C12 | 127.82 (15) | C15—C14—C11 | 121.1 (2) |
| C8—C7—C12 | 125.33 (15) | C15—C14—H14 | 119.5 |
| C13—C12—C11 | 120.13 (17) | C11—C14—H14 | 119.5 |
| C13—C12—C7 | 124.38 (17) | C16—C15—C14 | 120.1 (2) |
| C11—C12—C7 | 115.47 (16) | C16—C15—H15 | 120.0 |
| C7—C8—C6 | 105.03 (14) | C14—C15—H15 | 120.0 |
| C7—C8—C9 | 120.04 (16) | C15—C16—C13 | 120.4 (2) |
| C6—C8—C9 | 134.91 (16) | C15—C16—H16 | 119.8 |
| N1—C6—C8 | 111.09 (15) | C13—C16—H16 | 119.8 |
| N1—C6—C5 | 119.20 (15) | C9—C10—C11 | 116.24 (18) |
| C8—C6—C5 | 129.68 (15) | C9—C10—H10A | 108.2 |
| C1—C4—C5 | 119.47 (17) | C11—C10—H10A | 108.2 |
| C1—C4—H4 | 120.3 | C9—C10—H10B | 108.2 |
| C5—C4—H4 | 120.3 | C11—C10—H10B | 108.2 |
| C10—C9—C8 | 110.47 (17) | H10A—C10—H10B | 107.4 |
| C10—C9—H9A | 109.6 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···N3i | 0.86 | 2.17 | 2.895 (2) | 141 |
| Symmetry codes: (i) x−1/2, −y+1/2, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···N3i | 0.86 | 2.17 | 2.895 (2) | 141 |
| Symmetry codes: (i) x−1/2, −y+1/2, −z. |
The authors gratefully acknowledge the Natural Science Foundation of China (No. 20767001), the International Collaborative Project of Guizhou Province, the Governor Foundation of Guizhou Province and the Natural Science Youth Foundation of Guizhou University (No. 2007–005) for financial support.
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Indazole derivatives exhibit variety of pharmacological properties such as anti-inflammatory (Bistochi et al., 1981), antitumor (Keppler et al., 1994), anti-HIV (Sun et al., 1997) and analgesic (Gomtsyan et al., 2008). Herein we present the crystal structure of the title indazole derivative.
The crystal structure of the title compound is represented in Fig. 1. the C10-containing cyclohexa-1,3-diene ring displays a screw-boat conformation, and the pyridine ring is twisted to pyrazole ring with a dihedral angle of 29.13 (9)°. Intermolecular N—H···N hydrogen bonding presents in the crystal structure (Table 1).