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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2449.
Published online 2008 November 26. doi:  10.1107/S1600536808038944
PMCID: PMC2960070

3-(4-Pyrid­yl)-4,5-dihydro-1H-benzo[g]indazole

Abstract

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.

Related literature

For general background to indazole derivatives and their pharmacological properties, see: Bistochi et al. (1981 [triangle]); Keppler & Hartmann (1994 [triangle]); Sun et al. (1997 [triangle]); Gomtsyan et al. (2008 [triangle]).

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Object name is e-64-o2449-scheme1.jpg

Experimental

Crystal data

  • C16H13N3
  • M r = 247.29
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2449-efi1.jpg
  • a = 15.306 (2) Å
  • b = 8.8368 (13) Å
  • c = 18.543 (3) Å
  • V = 2508.1 (6) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 293 (2) K
  • 0.22 × 0.19 × 0.18 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: none
  • 24926 measured reflections
  • 2217 independent reflections
  • 1978 reflections with I > 2σ(I)
  • R int = 0.036

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.130
  • S = 1.08
  • 2217 reflections
  • 172 parameters
  • H-atom parameters constrained
  • Δρmax = 0.44 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808038944/xu2463sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808038944/xu2463Isup2.hkl

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

Acknowledgments

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.

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

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).

Figures

Fig. 1.
The molecular structure of (I) showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Crystal data

C16H13N3F000 = 1040
Mr = 247.29Dx = 1.310 Mg m3
Orthorhombic, PbcaMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2217 reflections
a = 15.306 (2) Åθ = 2.2–25.0º
b = 8.8368 (13) ŵ = 0.08 mm1
c = 18.543 (3) ÅT = 293 (2) K
V = 2508.1 (6) Å3Block, colorless
Z = 80.22 × 0.19 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer1978 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.036
Monochromator: graphiteθmax = 25.0º
T = 293(2) Kθmin = 2.2º
[var phi] and ω scansh = −18→17
Absorption correction: nonek = −10→9
24926 measured reflectionsl = −22→22
2217 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.130  w = 1/[σ2(Fo2) + (0.0626P)2 + 0.7587P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
2217 reflectionsΔρmax = 0.44 e Å3
172 parametersΔρmin = −0.25 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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
N20.37603 (9)0.33266 (16)0.11204 (7)0.0442 (4)
H20.32990.38820.11240.053*
N10.43088 (9)0.32191 (17)0.05503 (8)0.0458 (4)
C20.65724 (12)0.2397 (2)−0.07332 (10)0.0563 (5)
H2A0.67470.3078−0.10870.068*
C110.41088 (14)0.1591 (2)0.29215 (10)0.0567 (5)
C50.56409 (10)0.18489 (19)0.02662 (9)0.0436 (4)
C70.40188 (10)0.24622 (18)0.16853 (9)0.0415 (4)
C120.36103 (11)0.2337 (2)0.23932 (9)0.0466 (4)
C80.47774 (11)0.17516 (19)0.14790 (9)0.0438 (4)
C60.49343 (10)0.22560 (19)0.07685 (9)0.0425 (4)
C40.60463 (11)0.0446 (2)0.02934 (10)0.0484 (4)
H40.5881−0.02610.06390.058*
C90.52238 (13)0.0675 (2)0.19845 (11)0.0631 (5)
H9A0.5018−0.03460.18950.076*
H9B0.58490.06960.18990.076*
C10.66954 (11)0.0109 (2)−0.01959 (10)0.0534 (5)
H10.6958−0.0838−0.01650.064*
N30.69715 (9)0.10469 (18)−0.07098 (8)0.0534 (4)
C30.59220 (12)0.2840 (2)−0.02683 (10)0.0528 (5)
H30.56720.3795−0.03110.063*
C130.27959 (13)0.2938 (2)0.25682 (11)0.0614 (5)
H130.24680.34340.22190.074*
C140.37630 (18)0.1460 (3)0.36132 (11)0.0726 (6)
H140.40820.09620.39680.087*
C150.29537 (18)0.2057 (3)0.37810 (12)0.0771 (7)
H150.27330.19590.42460.092*
C160.24751 (16)0.2795 (3)0.32620 (12)0.0761 (7)
H160.19320.32000.33780.091*
C100.50413 (16)0.1100 (3)0.27516 (12)0.0759 (7)
H10A0.54320.19180.28840.091*
H10B0.51830.02400.30550.091*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N20.0354 (7)0.0488 (8)0.0484 (8)0.0074 (6)−0.0015 (6)0.0005 (6)
N10.0395 (8)0.0497 (8)0.0480 (8)0.0035 (6)−0.0009 (6)0.0016 (6)
C20.0498 (11)0.0611 (12)0.0579 (11)−0.0071 (9)0.0052 (8)0.0048 (9)
C110.0704 (12)0.0498 (11)0.0499 (10)−0.0028 (9)−0.0010 (9)0.0031 (8)
C50.0331 (8)0.0480 (9)0.0496 (9)−0.0036 (7)−0.0023 (7)−0.0032 (7)
C70.0375 (9)0.0422 (9)0.0447 (9)−0.0016 (7)−0.0033 (7)−0.0008 (7)
C120.0474 (10)0.0449 (9)0.0474 (9)−0.0077 (8)0.0013 (7)−0.0040 (7)
C80.0379 (9)0.0430 (9)0.0504 (10)0.0011 (7)−0.0024 (7)0.0020 (7)
C60.0361 (8)0.0416 (9)0.0498 (9)−0.0019 (7)−0.0022 (7)0.0007 (7)
C40.0412 (9)0.0455 (10)0.0585 (10)−0.0024 (7)0.0045 (8)0.0002 (8)
C90.0590 (12)0.0645 (12)0.0658 (12)0.0145 (10)−0.0004 (9)0.0158 (10)
C10.0428 (10)0.0493 (10)0.0681 (12)−0.0001 (8)0.0046 (8)−0.0068 (9)
N30.0396 (8)0.0601 (10)0.0605 (9)−0.0063 (7)0.0053 (7)−0.0069 (7)
C30.0455 (10)0.0520 (11)0.0610 (11)0.0020 (8)0.0051 (8)0.0058 (9)
C130.0494 (11)0.0756 (13)0.0592 (11)−0.0032 (10)0.0058 (9)−0.0080 (10)
C140.0972 (18)0.0692 (14)0.0515 (11)−0.0096 (13)0.0013 (11)0.0068 (10)
C150.0888 (17)0.0870 (16)0.0554 (12)−0.0268 (14)0.0208 (12)−0.0080 (11)
C160.0628 (13)0.0966 (17)0.0689 (13)−0.0122 (12)0.0210 (11)−0.0184 (13)
C100.0849 (14)0.0828 (16)0.0600 (12)0.0256 (12)−0.0095 (11)0.0120 (11)

Geometric parameters (Å, °)

N2—N11.353 (2)C4—C11.378 (2)
N2—C71.356 (2)C4—H40.9300
N2—H20.8600C9—C101.497 (3)
N1—C61.343 (2)C9—H9A0.9700
C2—N31.341 (3)C9—H9B0.9700
C2—C31.374 (3)C1—N31.332 (2)
C2—H2A0.9300C1—H10.9300
C11—C141.393 (3)C3—H30.9300
C11—C121.406 (3)C13—C161.383 (3)
C11—C101.525 (3)C13—H130.9300
C5—C41.387 (2)C14—C151.382 (4)
C5—C31.391 (2)C14—H140.9300
C5—C61.472 (2)C15—C161.374 (4)
C7—C81.374 (2)C15—H150.9300
C7—C121.458 (2)C16—H160.9300
C12—C131.393 (3)C10—H10A0.9700
C8—C61.412 (2)C10—H10B0.9700
C8—C91.500 (2)
N1—N2—C7112.52 (13)C8—C9—H9A109.6
N1—N2—H2123.7C10—C9—H9B109.6
C7—N2—H2123.7C8—C9—H9B109.6
C6—N1—N2104.56 (13)H9A—C9—H9B108.1
N3—C2—C3124.28 (18)N3—C1—C4124.42 (18)
N3—C2—H2A117.9N3—C1—H1117.8
C3—C2—H2A117.9C4—C1—H1117.8
C14—C11—C12118.3 (2)C1—N3—C2115.61 (16)
C14—C11—C10121.50 (19)C2—C3—C5119.47 (18)
C12—C11—C10119.84 (17)C2—C3—H3120.3
C4—C5—C3116.76 (16)C5—C3—H3120.3
C4—C5—C6121.60 (16)C16—C13—C12120.0 (2)
C3—C5—C6121.63 (16)C16—C13—H13120.0
N2—C7—C8106.80 (14)C12—C13—H13120.0
N2—C7—C12127.82 (15)C15—C14—C11121.1 (2)
C8—C7—C12125.33 (15)C15—C14—H14119.5
C13—C12—C11120.13 (17)C11—C14—H14119.5
C13—C12—C7124.38 (17)C16—C15—C14120.1 (2)
C11—C12—C7115.47 (16)C16—C15—H15120.0
C7—C8—C6105.03 (14)C14—C15—H15120.0
C7—C8—C9120.04 (16)C15—C16—C13120.4 (2)
C6—C8—C9134.91 (16)C15—C16—H16119.8
N1—C6—C8111.09 (15)C13—C16—H16119.8
N1—C6—C5119.20 (15)C9—C10—C11116.24 (18)
C8—C6—C5129.68 (15)C9—C10—H10A108.2
C1—C4—C5119.47 (17)C11—C10—H10A108.2
C1—C4—H4120.3C9—C10—H10B108.2
C5—C4—H4120.3C11—C10—H10B108.2
C10—C9—C8110.47 (17)H10A—C10—H10B107.4
C10—C9—H9A109.6

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···N3i0.862.172.895 (2)141

Symmetry codes: (i) x−1/2, −y+1/2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2463).

References

  • Bistochi, G. A., De Meo, G., Pedini, M., Ricci, A., Brouilhet, H., Bucherie, S., Rabaud, M. & Jacquignon, P. (1981). Farmaco Ed. Sci.36, 315–333. [PubMed]
  • Bruker (2002). SMART and SAINT Bruker AXS, Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Gomtsyan, A., Bayburt, E. K., Schmidt, R. G., Surowy, C. S., Honore, P., Marsh, K. C., Hannick, S. M., McDonald, H. A., Wetter, J. M., Sullivan, J. P., Jarvis, M. F., Faltynek, C. R. & Lee, C. H. (2008). J. Med. Chem.51, 392–395. [PubMed]
  • Keppler, B. K. & Hartmann, M. (1994). Met. Based Drugs.1, 145–149. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sun, J. H., Teleha, C. A., Yan, J. S., Rodgers, J. D. & Nugiel, D. A. (1997). J. Org. Chem.62, 5627–5629.

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