organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

2-Methyl-6-nitro-2H-indazole

aSchool of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300160, People's Republic of China, and bTianjin Institute of Pharmaceutical Research, Tianjin, 300193, People's Republic of China
*Correspondence e-mail: liudk@tjipr.com

(Received 18 May 2011; accepted 23 May 2011; online 28 May 2011)

In the title compound, C8H7N3O2, the mol­ecular skeleton is almost planar with a maximum deviation of 0.0484 (9) Å for the methyl C atom. In the crystal, weak inter­molecular C—H⋯N and C—H⋯O hydrogen bonds help to establish the packing.

Related literature

For the synthesis, see: Sorbera et al. (2006[Sorbera, L. A., Bolos, J. & Serradell, N. (2006). Drugs, 31, 585-589.]); Balardi et al. (1997[Balardi, P. G., Cacciari, B., Spalluto, G., Romagnoli, R., Braccioli, G., Zaid, A. N. & Pineda de las Infantas, M. J. (1997). Synthesis, 10, 1140-1142.]). For related structures, see: Qi et al. (2010[Qi, H.-F., Liu, B.-N., Liu, M. & Liu, D.-K. (2010). Acta Cryst. E66, o2955.]); Chen et al. (2009[Chen, Y., Fang, Z. & Wei, P. (2009). Acta Cryst. E65, o1775.]). For applications of indazole derivatives, see, for example: Li et al. (2008[Li, X. L., Wang, Y. B., Chen, H., Zhao, L. & Cao, K. Q. (2008). J. Hebei Univ. 28, 40-45.]).

[Scheme 1]

Experimental

Crystal data
  • C8H7N3O2

  • Mr = 177.17

  • Monoclinic, P 21 /c

  • a = 3.793 (3) Å

  • b = 12.200 (8) Å

  • c = 16.675 (11) Å

  • β = 95.722 (9)°

  • V = 767.7 (9) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.12 mm−1

  • T = 113 K

  • 0.40 × 0.20 × 0.10 mm

Data collection
  • Rigaku Saturn724 CCD diffractometer

  • Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005[Rigaku/MSC (2005). CrystalClear and CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.]) Tmin = 0.956, Tmax = 0.989

  • 7726 measured reflections

  • 1802 independent reflections

  • 1317 reflections with I > 2σ(I)

  • Rint = 0.039

Refinement
  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 0.092

  • S = 1.03

  • 1802 reflections

  • 119 parameters

  • H-atom parameters constrained

  • Δρmax = 0.28 e Å−3

  • Δρmin = −0.23 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C2—H2⋯N2i 0.95 2.52 3.446 (2) 164
C7—H7⋯O2ii 0.95 2.56 3.500 (2) 169
C8—H8A⋯O2iii 0.98 2.61 3.549 (2) 161
C8—H8B⋯O1ii 0.98 2.51 3.491 (2) 174
Symmetry codes: (i) -x, -y, -z+2; (ii) [x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]; (iii) -x+1, -y, -z+2.

Data collection: CrystalClear (Rigaku/MSC, 2005[Rigaku/MSC (2005). CrystalClear and CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005[Rigaku/MSC (2005). CrystalClear and CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.]).

Supporting information


Comment top

Some derivatives of indazole are important intermediates in the synthesis of drugs (Li et al. 2008). Herewith we report the crystal structure of the tile compound (I), which is an intermediate in the synthesis of the antitumor agent pazopanib.

In (I) (Fig. 1), the bond lengths and angles are normal and comparable with those reported for related compounds (Qi et al., 2010; Chen et al., 2009). Rings N2/N3/C7/C6/C1 and C1—C6 are almost coplanar forming a dihedral angle 1.08 (7) °. The indazole ring system is almost planar with the maximal deviation of 0.0118 (7) Å for atom N3. Nitro group is twisted at 0.93 (16)° from the plane of the attached indazole ring system.

In the crystal structure, weak intermolecular C—H···N and C—H···O hydrogen bonds (Table 1) help to establish the packing.

Related literature top

For the synthesis, see: Sorbera et al. (2006); Balardi et al. (1997). For related structures, see: Qi et al. (2010); Chen et al. (2009). For applications of indazole derivatives, see, for example: Li et al. (2008).

Experimental top

The title compound was prepared according to Sorbera et al. (2006) and Balardi et al. (1997). 6-Nitro-1H-indazole (2 g) was dissolved in regurgitant dichloromethane (30 ml), then dimethyl sulfate (1.7 ml) and dimethyl sulfoxide (2 ml) were introduced. The mixture was heated to reflux and stayed for 12 h. The reaction mixture was washed with saturated sodium bicarbonate (10 ml) and then extracted with dichloromethane (20 ml), dried with sodium sulfate and evaporated, to give yellow solid (78% yield). Crystals suitable for X-ray analysis were obtained by slow evaporation of a dichloromethane.

Refinement top

H atoms were positioned geometrically, with C—H = 0.95 and 0.98 Å for indazole and methyl H, and refined as riding atoms, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl).

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: CrystalStructure (Rigaku/MSC, 2005).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with the atom-numbering scheme and 50% probability displacement ellipsoids.
2-Methyl-6-nitro-2H-indazole top
Crystal data top
C8H7N3O2F(000) = 368
Mr = 177.17Dx = 1.533 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2636 reflections
a = 3.793 (3) Åθ = 2.1–28.0°
b = 12.200 (8) ŵ = 0.12 mm1
c = 16.675 (11) ÅT = 113 K
β = 95.722 (9)°Prism, colourless
V = 767.7 (9) Å30.40 × 0.20 × 0.10 mm
Z = 4
Data collection top
Rigaku Saturn724 CCD
diffractometer
1802 independent reflections
Radiation source: rotating anode1317 reflections with I > 2σ(I)
Multilayer monochromatorRint = 0.039
Detector resolution: 14.22 pixels mm-1θmax = 27.9°, θmin = 2.1°
ω and ϕ scansh = 44
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)
k = 1516
Tmin = 0.956, Tmax = 0.989l = 2121
7726 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.05P)2]
where P = (Fo2 + 2Fc2)/3
1802 reflections(Δ/σ)max = 0.001
119 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C8H7N3O2V = 767.7 (9) Å3
Mr = 177.17Z = 4
Monoclinic, P21/cMo Kα radiation
a = 3.793 (3) ŵ = 0.12 mm1
b = 12.200 (8) ÅT = 113 K
c = 16.675 (11) Å0.40 × 0.20 × 0.10 mm
β = 95.722 (9)°
Data collection top
Rigaku Saturn724 CCD
diffractometer
1802 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)
1317 reflections with I > 2σ(I)
Tmin = 0.956, Tmax = 0.989Rint = 0.039
7726 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.092H-atom parameters constrained
S = 1.03Δρmax = 0.28 e Å3
1802 reflectionsΔρmin = 0.23 e Å3
119 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
xyzUiso*/Ueq
O10.0001 (2)0.40192 (7)1.13521 (6)0.0330 (3)
O20.1008 (2)0.23042 (7)1.15673 (5)0.0285 (2)
N10.0034 (2)0.30444 (8)1.11496 (6)0.0204 (2)
N20.2860 (2)0.04933 (8)0.90394 (6)0.0191 (2)
N30.4265 (2)0.07413 (8)0.83460 (6)0.0189 (2)
C10.2577 (3)0.14834 (9)0.93942 (7)0.0164 (3)
C20.1284 (3)0.16936 (9)1.01433 (7)0.0172 (3)
H20.04260.11281.04630.021*
C30.1351 (3)0.27717 (9)1.03783 (7)0.0172 (3)
C40.2556 (3)0.36516 (9)0.99200 (7)0.0197 (3)
H40.25210.43801.01200.024*
C50.3767 (3)0.34458 (9)0.91902 (7)0.0202 (3)
H50.45650.40260.88740.024*
C60.3805 (3)0.23462 (9)0.89161 (7)0.0175 (3)
C70.4868 (3)0.18162 (9)0.82402 (7)0.0197 (3)
H70.58270.21470.77940.024*
C80.5084 (3)0.01456 (9)0.78106 (8)0.0225 (3)
H8A0.65890.06870.81140.034*
H8B0.63350.01500.73720.034*
H8C0.28790.04970.75860.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0491 (6)0.0212 (5)0.0301 (5)0.0001 (4)0.0114 (4)0.0077 (4)
O20.0399 (5)0.0249 (5)0.0227 (5)0.0030 (4)0.0126 (4)0.0002 (4)
N10.0211 (5)0.0207 (5)0.0195 (5)0.0007 (4)0.0026 (4)0.0017 (4)
N20.0233 (5)0.0198 (5)0.0149 (5)0.0002 (4)0.0058 (4)0.0000 (4)
N30.0200 (5)0.0216 (5)0.0155 (5)0.0003 (4)0.0040 (4)0.0004 (4)
C10.0147 (5)0.0172 (5)0.0171 (6)0.0000 (4)0.0004 (4)0.0013 (4)
C20.0182 (6)0.0172 (5)0.0163 (6)0.0002 (4)0.0021 (5)0.0013 (4)
C30.0155 (6)0.0203 (6)0.0158 (6)0.0016 (4)0.0018 (5)0.0004 (5)
C40.0194 (6)0.0161 (6)0.0235 (6)0.0009 (4)0.0010 (5)0.0008 (5)
C50.0194 (6)0.0189 (6)0.0222 (6)0.0015 (5)0.0026 (5)0.0046 (5)
C60.0151 (6)0.0208 (6)0.0163 (6)0.0002 (4)0.0008 (4)0.0027 (5)
C70.0193 (6)0.0218 (6)0.0185 (6)0.0013 (5)0.0036 (5)0.0033 (5)
C80.0262 (6)0.0234 (6)0.0190 (6)0.0016 (5)0.0073 (5)0.0029 (5)
Geometric parameters (Å, º) top
O1—N11.2367 (14)C3—C41.4194 (17)
O2—N11.2294 (14)C4—C51.3662 (19)
N1—C31.4639 (17)C4—H40.9500
N2—C11.3539 (16)C5—C61.4178 (17)
N2—N31.3547 (15)C5—H50.9500
N3—C71.3459 (17)C6—C71.3934 (18)
N3—C81.4559 (16)C7—H70.9500
C1—C21.4102 (18)C8—H8A0.9800
C1—C61.4265 (17)C8—H8B0.9800
C2—C31.3719 (17)C8—H8C0.9800
C2—H20.9500
O2—N1—O1122.63 (11)C5—C4—H4120.2
O2—N1—C3119.20 (10)C3—C4—H4120.2
O1—N1—C3118.17 (10)C4—C5—C6118.44 (11)
C1—N2—N3103.23 (10)C4—C5—H5120.8
C7—N3—N2114.58 (10)C6—C5—H5120.8
C7—N3—C8126.47 (11)C7—C6—C5135.47 (11)
N2—N3—C8118.91 (10)C7—C6—C1104.27 (11)
N2—C1—C2126.80 (10)C5—C6—C1120.25 (11)
N2—C1—C6111.69 (11)N3—C7—C6106.23 (11)
C2—C1—C6121.50 (11)N3—C7—H7126.9
C3—C2—C1115.41 (10)C6—C7—H7126.9
C3—C2—H2122.3N3—C8—H8A109.5
C1—C2—H2122.3N3—C8—H8B109.5
C2—C3—C4124.70 (12)H8A—C8—H8B109.5
C2—C3—N1118.07 (10)N3—C8—H8C109.5
C4—C3—N1117.22 (10)H8A—C8—H8C109.5
C5—C4—C3119.69 (11)H8B—C8—H8C109.5
C1—N2—N3—C70.23 (12)N1—C3—C4—C5179.08 (10)
C1—N2—N3—C8177.69 (9)C3—C4—C5—C60.52 (16)
N3—N2—C1—C2179.34 (10)C4—C5—C6—C7178.43 (12)
N3—N2—C1—C60.13 (12)C4—C5—C6—C10.46 (16)
N2—C1—C2—C3178.46 (10)N2—C1—C6—C70.01 (12)
C6—C1—C2—C30.96 (15)C2—C1—C6—C7179.51 (10)
C1—C2—C3—C40.92 (16)N2—C1—C6—C5179.19 (9)
C1—C2—C3—N1179.81 (9)C2—C1—C6—C50.31 (16)
O2—N1—C3—C21.59 (15)N2—N3—C7—C60.24 (12)
O1—N1—C3—C2178.04 (10)C8—N3—C7—C6177.50 (10)
O2—N1—C3—C4179.44 (9)C5—C6—C7—N3178.87 (12)
O1—N1—C3—C40.93 (14)C1—C6—C7—N30.14 (11)
C2—C3—C4—C50.19 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···N2i0.952.523.446 (2)164
C7—H7···O2ii0.952.563.500 (2)169
C8—H8A···O2iii0.982.613.549 (2)161
C8—H8B···O1ii0.982.513.491 (2)174
Symmetry codes: (i) x, y, z+2; (ii) x+1, y+1/2, z1/2; (iii) x+1, y, z+2.

Experimental details

Crystal data
Chemical formulaC8H7N3O2
Mr177.17
Crystal system, space groupMonoclinic, P21/c
Temperature (K)113
a, b, c (Å)3.793 (3), 12.200 (8), 16.675 (11)
β (°) 95.722 (9)
V3)767.7 (9)
Z4
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.40 × 0.20 × 0.10
Data collection
DiffractometerRigaku Saturn724 CCD
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku/MSC, 2005)
Tmin, Tmax0.956, 0.989
No. of measured, independent and
observed [I > 2σ(I)] reflections
7726, 1802, 1317
Rint0.039
(sin θ/λ)max1)0.659
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.092, 1.03
No. of reflections1802
No. of parameters119
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.28, 0.23

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

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···N2i0.952.523.446 (2)164
C7—H7···O2ii0.952.563.500 (2)169
C8—H8A···O2iii0.982.613.549 (2)161
C8—H8B···O1ii0.982.513.491 (2)174
Symmetry codes: (i) x, y, z+2; (ii) x+1, y+1/2, z1/2; (iii) x+1, y, z+2.
 

Acknowledgements

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

References

First citationBalardi, P. G., Cacciari, B., Spalluto, G., Romagnoli, R., Braccioli, G., Zaid, A. N. & Pineda de las Infantas, M. J. (1997). Synthesis, 10, 1140–1142.
First citationChen, Y., Fang, Z. & Wei, P. (2009). Acta Cryst. E65, o1775.  Web of Science CSD CrossRef IUCr Journals
First citationLi, X. L., Wang, Y. B., Chen, H., Zhao, L. & Cao, K. Q. (2008). J. Hebei Univ. 28, 40–45.
First citationQi, H.-F., Liu, B.-N., Liu, M. & Liu, D.-K. (2010). Acta Cryst. E66, o2955.  Web of Science CSD CrossRef IUCr Journals
First citationRigaku/MSC (2005). CrystalClear and CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSorbera, L. A., Bolos, J. & Serradell, N. (2006). Drugs, 31, 585–589.  CAS

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ISSN: 2056-9890
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