1-Methyl-1H-indazole-3-carboxylic acid.

Abstract

The asymmetric unit of the title compound, C(9)H(8)N(2)O(2), contains two mol-ecules. In the crystal structure, both mol-ecules form inversion dimers via pairs of O-H⋯O hydrogen bonds, and a C-H⋯O inter-ation is also seen.

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1-Methyl-1H-indazole-3-carboxylic acid
Si-shun Kang,aHong-wei Wang,bMin Zhang,aRan-zhe
Luaand Hai-bo Wanga*
aCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5
Nanjing, Nanjing 210009, People’s Republic of China, andbNantong Entry–Exit
Inspection and Quarantine Bureau, Nantong 226005, People’s Republic of China
Correspondence e-mail: wanghaibo@njut.edu.cn
Received 27 October 2008; accepted 30 October 2008
Key indicators: single-crystal X-ray study; T = 293 K; mean ?(C–C) = 0.004 A ˚;
R factor = 0.058; wR factor = 0.143; data-to-parameter ratio = 12.8.
The asymmetric unit of the title compound, C9H8N2O2,
contains two molecules. In the crystal structure, both mol-
ecules form inversion dimers via pairs of O—H???O hydrogen
bonds, and a C—H???O interation is also seen.
Related literature
For the synthesis, see: Rousseau & Lindwall (1950).
Experimental
Crystal data
C9H8N2O2
Mr= 176.17
Monoclinic, P21=n
a = 7.5470 (15) A˚
b = 14.873 (3) A˚
c = 14.924 (3) A˚
? = 93.10 (3)?
V = 1672.7 (6) A˚3
Z = 8
Mo K? radiation
? = 0.10 mm?1
T = 293 (2) K
0.30 ? 0.20 ? 0.10 mm
Data collection
Enraf–Nonius CAD-4
diffractometer
Absorption correction: scan
(North et al., 1968)
Tmin= 0.970, Tmax= 0.990
3273 measured reflections
3032 independent reflections
1955 reflections with I > 2?(I)
Rint= 0.0225
3 standard reflections
every 200 reflections
intensity decay: 1%
Refinement
R[F2> 2?(F2)] = 0.058
wR(F2) = 0.143
S = 1.00
3032 reflections
237 parameters
H-atom parameters constrained
??max= 0.18 e A˚?3
??min= ?0.21 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
O2—H2A???O1i
O3—H3A???O4ii
C8—H8A???O1iii
Symmetry
x þ1
D—HH???AD???AD—H???A
0.82
0.82
0.93
1.82
1.82
2.52
2.632 (3)
2.619 (3)
3.293 (4)
173
164
140
codes:
2;z ?1
(i)
?x;?y þ 1;?z þ 1;(ii)
?x þ 1;?y þ 1;?z þ 1;(iii)
2;?y þ1
2.
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell
refinement: CAD-4 Software; data reduction: XCAD4 (Harms &
Wocadlo, 1995); 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: SHELXL97.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: HB2830).
References
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Nether-
lands.
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–
359.
Rousseau, V. & Lindwall, H. G. (1950). J. Am. Chem. Soc. 72, 3047–3051.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
organic compounds
Acta Cryst. (2008). E64, o2257 doi:10.1107/S160053680803554XKang et al.
o2257
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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supplementary materials

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supplementary materials
sup-1
Acta Cryst. (2008). E64, o2257 [ doi:10.1107/S160053680803554X ]
1-Methyl-1H-indazole-3-carboxylic acid
S. Kang, H. Wang, M. Zhang, R. Lu and H. Wang
Comment
Methyl indazole carboxylic acid is an important pharmaceutical intermediate: many of its derivatives have biological activity
and be used as a variety of drugs. We report here the crystal structure of the title compound, (I). There are O—H···O
intermolecular H bonds in the structure between the hydrogencarboxylates forming the paired molecules that are situated
on the crystallographic inversion centres (Table 1). The molecular structure of (I) is shown in Fig. 1.
Experimental
We prepared the title compound according to the literature method (Rousseau & Lindwall, 1950). Colourless blocks of (I)
were obtained by slow evaporation of an petroleum/metanhol solution.
Refinement
The H atoms were placed geometrically (C—H = 0.93-0.97Å, O—H = 0.82Å) and refined as riding with Uiso(H) = 1.2
or 1.5Ueq(carrier).
Figures
Fig. 1. A view of the molecular structure of (I), showing displacement ellipsoids at the 30%
probability level (arbitrary spheres for the H atoms).
1-Methyl-1H-indazole-3-carboxylic acid
Crystal data
C9H8N2O2
F000 = 736
Dx = 1.399 Mg m−3
Mo Kα radiation
λ = 0.71073 Å
Cell parameters from 25 reflections
θ = 9–13º
µ = 0.10 mm−1
Mr = 176.17
Monoclinic, P21/n
Hall symbol: -P 2yn
a = 7.5470 (15) Å
b = 14.873 (3) Å

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supplementary materials
sup-2
c = 14.924 (3) Å
β = 93.10 (3)º
V = 1672.7 (6) Å3
Z = 8
T = 293 (2) K
Block, colorless
0.30 × 0.20 × 0.10 mm
Data collection
Enraf–Nonius CAD-4
diffractometer
Radiation source: fine-focus sealed tube
Monochromator: graphite
T = 293(2) K
ω/2θ scans
Absorption correction: ψ scan
(North et al., 1968)
Tmin = 0.970, Tmax = 0.990
3273 measured reflections
3032 independent reflections
1955 reflections with I > 2σ(I)
Rint = 0.023
θmax = 25.3º
θmin = 1.9º
h = −9→9
k = 0→17
l = 0→17
3 standard reflections
every 200 reflections
intensity decay: 1%
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)] = 0.058
H-atom parameters constrained
wR(F2) = 0.143
w = 1/[σ2(Fo2) + (0.05P)2 + 1.2P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.007
Δρmax = 0.18 e Å−3
Δρmin = −0.21 e Å−3
S = 1.00
3032 reflections
237 parameters
Primary atom site location: structure-invariant direct
methods
Extinction 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 mat-
rix. 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, convention-
al 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.

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supplementary materials
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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
−0.0113 (3)
0.0844 (3)
0.0587
0.0777 (3)
0.0425 (3)
0.0605 (5)
0.0634
−0.0500
0.1569
0.0474 (4)
0.0726 (3)
0.1346 (3)
0.1353 (3)
0.1899 (3)
0.1896
0.2442 (4)
0.2834
0.2429 (4)
0.2790
0.1899 (4)
0.1896
0.4920 (3)
0.4752
0.5840 (3)
0.6825 (3)
0.6574 (3)
0.7390 (4)
0.7340
0.8584
0.6618
0.5579 (3)
0.5990 (3)
0.5881 (3)
0.6464 (4)
0.6532 (4)
0.6879
0.6078 (4)
0.6139
0.5502 (4)
0.5181
0.5410 (4)
0.5050
y
0.38836 (12)
0.46943 (12)
0.5109
0.17493 (14)
0.23313 (15)
0.07913 (19)
0.0488
0.0667
0.0583
0.39448 (17)
0.31492 (17)
0.31004 (17)
0.21700 (18)
0.37047 (19)
0.4321
0.3372 (2)
0.3769
0.2443 (2)
0.2240
0.1841 (2)
0.1228
0.38818 (12)
0.4303
0.50052 (13)
0.30394 (16)
0.37909 (15)
0.3098 (2)
0.2512
0.3321
0.3499
0.41736 (17)
0.35246 (17)
0.25681 (17)
0.22852 (19)
0.1370 (2)
0.1192
0.0772 (2)
0.0163
0.1039 (2)
0.0600
0.19292 (18)
0.2101
z
0.50834 (13)
0.39536 (13)
0.4284
0.34517 (17)
0.41044 (16)
0.3588 (3)
0.3021
0.3852
0.3980
0.43217 (19)
0.37687 (17)
0.28951 (17)
0.27100 (19)
0.22478 (18)
0.2355
0.1459 (2)
0.1030
0.1273 (2)
0.0722
0.1883 (2)
0.1761
0.47829 (12)
0.5122
0.39334 (14)
0.21444 (15)
0.26119 (15)
0.12273 (19)
0.0957
0.1234
0.0887
0.40759 (18)
0.33950 (17)
0.34408 (18)
0.26155 (19)
0.2374 (2)
0.1813
0.2984 (3)
0.2849
0.3838 (2)
0.4243
0.4077 (2)
0.4638
Uiso*/Ueq
0.0608 (6)
0.0627 (6)
0.094*
0.0511 (6)
0.0491 (6)
0.0738 (10)
0.111*
0.111*
0.111*
0.0451 (7)
0.0402 (6)
0.0398 (6)
0.0444 (7)
0.0478 (7)
0.057*
0.0593 (8)
0.071*
0.0620 (9)
0.074*
0.0604 (9)
0.073*
0.0587 (6)
0.088*
0.0655 (6)
0.0519 (6)
0.0474 (6)
0.0672 (9)
0.101*
0.101*
0.101*
0.0433 (7)
0.0380 (6)
0.0406 (6)
0.0465 (7)
0.0616 (9)
0.074*
0.0677 (10)
0.081*
0.0669 (9)
0.080*
0.0531 (7)
0.064*
O1
O2
H2A
N1
N2
C1
H1A
H1B
H1C
C2
C3
C4
C5
C6
H6A
C7
H7A
C8
H8A
C9
H9A
O3
H3A
O4
N3
N4
C10
H10A
H10B
H10C
C11
C12
C13
C14
C15
H15A
C16
H16A
C17
H17A
C18
H18A