1,3-Dimethyl-1H-indazol-6-amine

Zhang, X.-K.; Liu, B.-N.; Liu, M.; Liu, D.-K.; Wang, P.-B.

doi:10.1107/S1600536812013694

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1291

doi:10.1107/S1600536812013694

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1,3-Dimethyl-1H-indazol-6-amine

Xiao-Kai Zhang,^a Bing-Ni Liu,^b ^* Mo Liu,^b Deng-Ke Liu ^b and Ping-Bao Wang ^c

^aPharmaceutical College of Henan University, Henan Kaifeng 475000, People's Republic of China, ^bTianjin Institute of Pharmaceutical Research, Tianjin 300193, People's Republic of China, and ^cTianjin Tnstitute of Pharmaceutical Rearch, Tianjin 300193, People's Republic of China
^*Correspondence e-mail: liubn@tjipr.com

(Received 27 March 2012; accepted 29 March 2012; online 4 April 2012)

The molecular skeleton of the title compound, C₉H₁₁N₃, is almost planar, with a maximum deviation of 0.0325 (19) Å for the amino N atom. In the crystal, N—H⋯N hydrogen bonds establish the packing.

Related literature

For the synthesis of the title compound, see: Sorbera et al. (2006 ); Zhao et al. (2011 ). For related structures, see: Qi et al.(2010 ); Long et al. (2011 ). For the application of indazole derivatives in the synthesis of drugs, see: Collot et al. (1999 ).

Experimental

Crystal data

C₉H₁₁N₃
M_r = 161.21
Orthorhombic, P c a 2₁
a = 18.3004 (10) Å
b = 8.3399 (7) Å
c = 5.6563 (1) Å
V = 863.28 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.22 × 0.18 × 0.12 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.983, T_max = 0.991
7967 measured reflections
2002 independent reflections
1588 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.149
S = 1.02
2002 reflections
118 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N1ⁱ	0.89 (1)	2.32 (1)	3.203 (2)	169 (2)
N3—H3B⋯N3ⁱⁱ	0.91 (1)	2.48 (1)	3.384 (2)	175 (2)
Symmetry codes: (i) x, y-1, z; (ii) $[-x+{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812013694/kp2401sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812013694/kp2401Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812013694/kp2401Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536812013694/kp2401Isup4.cml

checkCIF report

Comment top

Some derivatives of indazole are important intermediates in the synthesis of drugs (Collot et al.1999). Here we report the crystal structure of the title compound(I).

In (I) the bond lengths and angles are normal and comparable with those reported for related compounds (Long et al.,2011; Qi et al., 2010). The rings C3/C4/C5/C6/C7/C8 and C3/C2/N1/N2/C8 are almost coplaner forming a dihedral angle 0.82 (14)° (Fig. 1). The indazole ring system is almost planar with the maximal deviation of 0.0325 (19) Å for the atom N3. In the crystal structure intermolecular N–H···N hydrogen bonds (Fig. 2, Table 1) establish the packing.

Related literature top

For the synthesis of the title compound, see: Sorbera et al. (2006); Zhao et al. (2011). For related structures, see: Qi et al.(2010); Long et al. (2011). For the application of indazole derivatives in the synthesis of drugs, see: Collot et al. (1999).

Experimental top

Step 1: Dimethyl carbonate(7.5 g, 3 eq) was added to a solution of 3-methyl-6-nitro-1H-indazole(5 g, 1eq) and triethylene diamine(3.1 g, 1eq) in 15 mL DMF. After stirring of 10 h at 353 K, the mixture was poured into 150 mL cold water, after filtering and drying a mixture of 1,3-dimethyl-6-nitro-1H-indazole and 2,3-dimethyl -6-nitro-2H-indazole were obtained.1,3-Dimethyl-6-nitro-1H- indazole (2 g) was obtained by silicagel column chromatography.

Step 2: Pd/C(0.2 g) was added to a solution of 1,3-dimethyl-6-nitro-1H-indazole (2 g) in 10 mL ethanol. After the reaction system was kept in vacuum, the mixture was treated with continuous hydrogen stream. After stirring of 8 h, the reaction system was filtered to get yellow solution. The solution was left at room temperature, and colourless crystals were grown slowly.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 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).

Figures top

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme and 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram for (I) with hydrogen bonds (dashed lines).

1,3-Dimethyl-1H-indazol-6-amine top

Crystal data top

C₉H₁₁N₃	F(000) = 344
M_r = 161.21	D_x = 1.240 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 2241 reflections
a = 18.3004 (10) Å	θ = 3.3–27.9°
b = 8.3399 (7) Å	µ = 0.08 mm⁻¹
c = 5.6563 (1) Å	T = 293 K
V = 863.28 (9) Å³	Prism, yellow
Z = 4	0.22 × 0.18 × 0.12 mm

Data collection top

Rigaku Saturn diffractometer	2002 independent reflections
Radiation source: rotating anode	1588 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.045
ω scans	θ_max = 27.8°, θ_min = 2.7°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	h = −23→24
T_min = 0.983, T_max = 0.991	k = −9→10
7967 measured reflections	l = −7→7

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.149	w = 1/[σ²(F_o²) + (0.0907P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.002
2002 reflections	Δρ_max = 0.16 e Å⁻³
118 parameters	Δρ_min = −0.14 e Å⁻³
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.12 (2)

Crystal data top

C₉H₁₁N₃	V = 863.28 (9) Å³
M_r = 161.21	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 18.3004 (10) Å	µ = 0.08 mm⁻¹
b = 8.3399 (7) Å	T = 293 K
c = 5.6563 (1) Å	0.22 × 0.18 × 0.12 mm

Data collection top

Rigaku Saturn diffractometer	2002 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1588 reflections with I > 2σ(I)
T_min = 0.983, T_max = 0.991	R_int = 0.045
7967 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	4 restraints
wR(F²) = 0.149	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.16 e Å⁻³
2002 reflections	Δρ_min = −0.14 e Å⁻³
118 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
N1	0.10351 (9)	0.83358 (18)	0.4784 (4)	0.0568 (5)
N2	0.14711 (8)	0.72497 (19)	0.5968 (4)	0.0538 (5)
N3	0.19922 (10)	0.1548 (2)	0.4581 (5)	0.0699 (6)
H3A	0.1689 (11)	0.071 (2)	0.449 (5)	0.084*
H3B	0.2287 (12)	0.150 (3)	0.587 (3)	0.084*
C1	0.01866 (14)	0.8321 (3)	0.1420 (6)	0.0785 (8)
H1A	−0.0293	0.7890	0.1680	0.118*
H1B	0.0330	0.8131	−0.0188	0.118*
H1C	0.0182	0.9454	0.1721	0.118*
C2	0.07147 (10)	0.7530 (3)	0.3043 (5)	0.0549 (5)
C3	0.09469 (10)	0.5900 (2)	0.3044 (4)	0.0493 (5)
C4	0.08096 (11)	0.4531 (3)	0.1658 (5)	0.0596 (6)
H4	0.0489	0.4579	0.0384	0.072*
C5	0.11558 (12)	0.3130 (3)	0.2223 (5)	0.0615 (6)
H5	0.1072	0.2228	0.1295	0.074*
C6	0.16353 (10)	0.3008 (2)	0.4163 (5)	0.0559 (6)
C7	0.17824 (11)	0.4336 (2)	0.5559 (4)	0.0529 (5)
H7	0.2102	0.4277	0.6836	0.063*
C8	0.14298 (9)	0.5768 (2)	0.4964 (4)	0.0472 (5)
C9	0.19061 (12)	0.7763 (3)	0.7940 (5)	0.0624 (6)
H9A	0.1936	0.6913	0.9081	0.094*
H9B	0.1685	0.8688	0.8655	0.094*
H9C	0.2388	0.8032	0.7402	0.094*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0555 (9)	0.0501 (9)	0.0648 (12)	0.0046 (6)	−0.0046 (8)	−0.0011 (9)
N2	0.0544 (8)	0.0497 (9)	0.0573 (10)	0.0024 (7)	−0.0077 (8)	−0.0037 (8)
N3	0.0716 (13)	0.0426 (9)	0.0956 (17)	−0.0012 (7)	−0.0004 (12)	0.0028 (11)
C1	0.0711 (14)	0.0782 (15)	0.0862 (19)	0.0149 (11)	−0.0214 (14)	0.0054 (14)
C2	0.0474 (9)	0.0563 (11)	0.0610 (12)	0.0026 (8)	−0.0019 (9)	0.0031 (10)
C3	0.0462 (9)	0.0521 (11)	0.0496 (11)	−0.0036 (7)	−0.0001 (8)	0.0017 (9)
C4	0.0581 (11)	0.0599 (12)	0.0608 (13)	−0.0082 (9)	−0.0086 (10)	−0.0051 (11)
C5	0.0655 (12)	0.0509 (11)	0.0682 (15)	−0.0097 (9)	−0.0008 (11)	−0.0082 (10)
C6	0.0517 (10)	0.0463 (10)	0.0696 (15)	−0.0031 (8)	0.0064 (10)	0.0027 (10)
C7	0.0509 (9)	0.0495 (11)	0.0581 (12)	−0.0016 (7)	0.0008 (9)	0.0074 (9)
C8	0.0429 (8)	0.0461 (10)	0.0526 (11)	−0.0025 (6)	0.0018 (8)	0.0037 (9)
C9	0.0663 (13)	0.0651 (13)	0.0556 (13)	−0.0020 (10)	−0.0097 (10)	−0.0054 (11)

Geometric parameters (Å, º) top

N1—C2	1.329 (3)	C3—C8	1.404 (3)
N1—N2	1.380 (2)	C3—C4	1.407 (3)
N2—C8	1.362 (2)	C4—C5	1.367 (3)
N2—C9	1.436 (3)	C4—H4	0.9300
N3—C6	1.401 (3)	C5—C6	1.409 (3)
N3—H3A	0.893 (9)	C5—H5	0.9300
N3—H3B	0.909 (10)	C6—C7	1.387 (3)
C1—C2	1.487 (3)	C7—C8	1.399 (3)
C1—H1A	0.9600	C7—H7	0.9300
C1—H1B	0.9600	C9—H9A	0.9600
C1—H1C	0.9600	C9—H9B	0.9600
C2—C3	1.424 (3)	C9—H9C	0.9600

C2—N1—N2	106.43 (17)	C5—C4—H4	120.6
C8—N2—N1	111.14 (17)	C3—C4—H4	120.6
C8—N2—C9	128.72 (17)	C4—C5—C6	122.2 (2)
N1—N2—C9	120.11 (17)	C4—C5—H5	118.9
C6—N3—H3A	112.3 (15)	C6—C5—H5	118.9
C6—N3—H3B	116.7 (15)	C7—C6—N3	120.5 (2)
H3A—N3—H3B	112.6 (15)	C7—C6—C5	120.41 (19)
C2—C1—H1A	109.5	N3—C6—C5	119.0 (2)
C2—C1—H1B	109.5	C6—C7—C8	117.1 (2)
H1A—C1—H1B	109.5	C6—C7—H7	121.4
C2—C1—H1C	109.5	C8—C7—H7	121.4
H1A—C1—H1C	109.5	N2—C8—C7	130.43 (19)
H1B—C1—H1C	109.5	N2—C8—C3	106.65 (16)
N1—C2—C3	110.53 (19)	C7—C8—C3	122.91 (18)
N1—C2—C1	121.3 (2)	N2—C9—H9A	109.5
C3—C2—C1	128.1 (2)	N2—C9—H9B	109.5
C8—C3—C4	118.65 (18)	H9A—C9—H9B	109.5
C8—C3—C2	105.24 (18)	N2—C9—H9C	109.5
C4—C3—C2	136.1 (2)	H9A—C9—H9C	109.5
C5—C4—C3	118.7 (2)	H9B—C9—H9C	109.5

C2—N1—N2—C8	0.5 (2)	N3—C6—C7—C8	177.1 (2)
C2—N1—N2—C9	178.8 (2)	C5—C6—C7—C8	0.7 (3)
N2—N1—C2—C3	−0.9 (2)	N1—N2—C8—C7	179.1 (2)
N2—N1—C2—C1	178.5 (2)	C9—N2—C8—C7	1.0 (3)
N1—C2—C3—C8	0.9 (2)	N1—N2—C8—C3	0.1 (2)
C1—C2—C3—C8	−178.4 (2)	C9—N2—C8—C3	−178.0 (2)
N1—C2—C3—C4	−178.9 (2)	C6—C7—C8—N2	−179.1 (2)
C1—C2—C3—C4	1.8 (4)	C6—C7—C8—C3	−0.2 (3)
C8—C3—C4—C5	−0.5 (3)	C4—C3—C8—N2	179.25 (18)
C2—C3—C4—C5	179.2 (2)	C2—C3—C8—N2	−0.6 (2)
C3—C4—C5—C6	1.0 (4)	C4—C3—C8—C7	0.2 (3)
C4—C5—C6—C7	−1.1 (3)	C2—C3—C8—C7	−179.67 (19)
C4—C5—C6—N3	−177.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1ⁱ	0.89 (1)	2.32 (1)	3.203 (2)	169 (2)
N3—H3B···N3ⁱⁱ	0.91 (1)	2.48 (1)	3.384 (2)	175 (2)

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

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃
M_r	161.21
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	293
a, b, c (Å)	18.3004 (10), 8.3399 (7), 5.6563 (1)
V (Å³)	863.28 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.22 × 0.18 × 0.12

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.983, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	7967, 2002, 1588
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.657

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.149, 1.02
No. of reflections	2002
No. of parameters	118
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.14

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1ⁱ	0.893 (9)	2.321 (12)	3.203 (2)	169 (2)
N3—H3B···N3ⁱⁱ	0.909 (10)	2.478 (10)	3.384 (2)	175 (2)

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

Acknowledgements

The authors thank Mr Hai-Bin Song of Nankai University for the X-ray crystallographic determination and helpful suggestions.

References

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