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

Abstract

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,

• a = 18.3004 (10) Å

• b = 8.3399 (7) Å

• c = 5.6563 (1) Å

• V = 863.28 (9) ų

• 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[F ² > 2σ(F ²)] = 0.055

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812013694/kp2401Isup3.cdx

Supplementary material file. DOI: 10.1107/S1600536812013694/kp2401Isup4.cml

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

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

C-bound H atoms were geometrically positioned (C—H 0.93–0.96 Å),and refined as riding with U_iso=1.2–1.5U_eq(C).

Figures

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).

Crystal data

C9H11N3	F(000) = 344
Mr = 161.21	Dx = 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

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

Refinement

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(Fo2) + (0.0907P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.002
2002 reflections	Δρmax = 0.16 e Å−3
118 parameters	Δρmin = −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)

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.