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

Xiao, X.; Zhang, Y.-Q.; Xue, S.-F.; Zhu, Q.-J.; Tao, Z.

doi:10.1107/S1600536808038944

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2449

doi:10.1107/S1600536808038944

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

Xin Xiao,^a Yun-Qiang Zhang,^a Sai-Feng Xue,^a Qian-Jiang Zhu ^a ^* and Zhu Tao ^b

^aKey Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Guizhou University, Guiyang 550025, People's Republic of China, and ^bInstitute of Applied Chemistry, Guizhou University, Guiyang 550025, People's Republic of China
^*Correspondence e-mail: gyhxxiaoxin@163.com

(Received 2 November 2008; accepted 20 November 2008; online 26 November 2008)

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 ); Keppler & Hartmann (1994 ); Sun et al. (1997 ); Gomtsyan et al. (2008 ).

Experimental

Crystal data

C₁₆H₁₃N₃
M_r = 247.29
Orthorhombic, P b c a
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[F² > 2σ(F²)] = 0.048
wR(F²) = 0.130
S = 1.08
2217 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N3ⁱ	0.86	2.17	2.895 (2)	141
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; 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 ).

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

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).

Figures top

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

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

Crystal data top

C₁₆H₁₃N₃	F(000) = 1040
M_r = 247.29	D_x = 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

Data collection top

Bruker SMART CCD area-detector diffractometer	1978 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.036
Graphite monochromator	θ_max = 25.0°, θ_min = 2.2°
ϕ and ω scans	h = −18→17
24926 measured reflections	k = −10→9
2217 independent reflections	l = −22→22

Refinement top

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(F_o²) + (0.0626P)² + 0.7587P] where P = (F_o² + 2F_c²)/3
2217 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₆H₁₃N₃	V = 2508.1 (6) Å³
M_r = 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

Data collection top

Bruker SMART CCD area-detector diffractometer	1978 reflections with I > 2σ(I)
24926 measured reflections	R_int = 0.036
2217 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.08	Δρ_max = 0.44 e Å⁻³
2217 reflections	Δρ_min = −0.25 e Å⁻³
172 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N3ⁱ	0.86	2.17	2.895 (2)	141

Symmetry code: (i) x−1/2, −y+1/2, −z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₃N₃
M_r	247.29
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	15.306 (2), 8.8368 (13), 18.543 (3)
V (Å³)	2508.1 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.22 × 0.19 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	24926, 2217, 1978
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.130, 1.08
No. of reflections	2217
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.25

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N3ⁱ	0.86	2.17	2.895 (2)	141.4

Symmetry code: (i) x−1/2, −y+1/2, −z.

Acknowledgements

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.

References

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