supplementary materials


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

Abstract top

The asymmetric unit of the title compound, C9H8N2O2, contains two molecules. In the crystal structure, both molecules form inversion dimers via pairs of O-H...O hydrogen bonds, and a C-H...O interation is also seen.

Comment top

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.

Related literature top

For the synthesis, see: Rousseau & Lindwall (1950).

Experimental top

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 top

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).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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 (Sheldrick, 2008).

Figures top
[Figure 1] 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 top
Crystal data top
C9H8N2O2F(000) = 736
Mr = 176.17Dx = 1.399 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 7.5470 (15) Åθ = 9–13°
b = 14.873 (3) ŵ = 0.10 mm1
c = 14.924 (3) ÅT = 293 K
β = 93.10 (3)°Block, colorless
V = 1672.7 (6) Å30.30 × 0.20 × 0.10 mm
Z = 8
Data collection top
Enraf–Nonius CAD-4
diffractometer
1955 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.023
graphiteθmax = 25.3°, θmin = 1.9°
ω/2θ scansh = 99
Absorption correction: ψ scan
(North et al., 1968)
k = 017
Tmin = 0.970, Tmax = 0.990l = 017
3273 measured reflections3 standard reflections every 200 reflections
3032 independent reflections intensity decay: 1%
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)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.05P)2 + 1.2P]
where P = (Fo2 + 2Fc2)/3
3032 reflections(Δ/σ)max = 0.007
237 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.21 e Å3
Crystal data top
C9H8N2O2V = 1672.7 (6) Å3
Mr = 176.17Z = 8
Monoclinic, P21/nMo Kα radiation
a = 7.5470 (15) ŵ = 0.10 mm1
b = 14.873 (3) ÅT = 293 K
c = 14.924 (3) Å0.30 × 0.20 × 0.10 mm
β = 93.10 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
1955 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.023
Tmin = 0.970, Tmax = 0.990θmax = 25.3°
3273 measured reflections3 standard reflections every 200 reflections
3032 independent reflections intensity decay: 1%
Refinement top
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.143Δρmax = 0.18 e Å3
S = 1.00Δρmin = 0.21 e Å3
3032 reflectionsAbsolute structure: ?
237 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
O10.0113 (3)0.38836 (12)0.50834 (13)0.0608 (6)
O20.0844 (3)0.46943 (12)0.39536 (13)0.0627 (6)
H2A0.05870.51090.42840.094*
N10.0777 (3)0.17493 (14)0.34517 (17)0.0511 (6)
N20.0425 (3)0.23313 (15)0.41044 (16)0.0491 (6)
C10.0605 (5)0.07913 (19)0.3588 (3)0.0738 (10)
H1A0.06340.04880.30210.111*
H1B0.05000.06670.38520.111*
H1C0.15690.05830.39800.111*
C20.0474 (4)0.39448 (17)0.43217 (19)0.0451 (7)
C30.0726 (3)0.31492 (17)0.37687 (17)0.0402 (6)
C40.1346 (3)0.31004 (17)0.28951 (17)0.0398 (6)
C50.1353 (3)0.21700 (18)0.27100 (19)0.0444 (7)
C60.1899 (3)0.37047 (19)0.22478 (18)0.0478 (7)
H6A0.18960.43210.23550.057*
C70.2442 (4)0.3372 (2)0.1459 (2)0.0593 (8)
H7A0.28340.37690.10300.071*
C80.2429 (4)0.2443 (2)0.1273 (2)0.0620 (9)
H8A0.27900.22400.07220.074*
C90.1899 (4)0.1841 (2)0.1883 (2)0.0604 (9)
H9A0.18960.12280.17610.073*
O30.4920 (3)0.38818 (12)0.47829 (12)0.0587 (6)
H3A0.47520.43030.51220.088*
O40.5840 (3)0.50052 (13)0.39334 (14)0.0655 (6)
N30.6825 (3)0.30394 (16)0.21444 (15)0.0519 (6)
N40.6574 (3)0.37909 (15)0.26119 (15)0.0474 (6)
C100.7390 (4)0.3098 (2)0.12273 (19)0.0672 (9)
H10A0.73400.25120.09570.101*
H10B0.85840.33210.12340.101*
H10C0.66180.34990.08870.101*
C110.5579 (3)0.41736 (17)0.40759 (18)0.0433 (7)
C120.5990 (3)0.35246 (17)0.33950 (17)0.0380 (6)
C130.5881 (3)0.25681 (17)0.34408 (18)0.0406 (6)
C140.6464 (4)0.22852 (19)0.26155 (19)0.0465 (7)
C150.6532 (4)0.1370 (2)0.2374 (2)0.0616 (9)
H15A0.68790.11920.18130.074*
C160.6078 (4)0.0772 (2)0.2984 (3)0.0677 (10)
H16A0.61390.01630.28490.081*
C170.5502 (4)0.1039 (2)0.3838 (2)0.0669 (9)
H17A0.51810.06000.42430.080*
C180.5410 (4)0.19292 (18)0.4077 (2)0.0531 (7)
H18A0.50500.21010.46380.064*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.1022 (16)0.0363 (11)0.0479 (12)0.0076 (11)0.0402 (11)0.0043 (9)
O20.1051 (18)0.0305 (11)0.0568 (12)0.0012 (11)0.0438 (12)0.0025 (9)
N10.0550 (15)0.0271 (12)0.0718 (17)0.0010 (10)0.0096 (12)0.0088 (11)
N20.0551 (15)0.0355 (13)0.0581 (15)0.0028 (11)0.0157 (12)0.0012 (11)
C10.081 (2)0.0279 (16)0.114 (3)0.0007 (16)0.016 (2)0.0012 (17)
C20.0571 (18)0.0305 (15)0.0490 (16)0.0005 (13)0.0142 (13)0.0002 (12)
C30.0432 (15)0.0302 (14)0.0486 (15)0.0013 (12)0.0164 (12)0.0019 (12)
C40.0373 (14)0.0384 (15)0.0442 (15)0.0003 (12)0.0076 (11)0.0119 (12)
C50.0376 (14)0.0370 (15)0.0588 (17)0.0082 (12)0.0053 (13)0.0111 (13)
C60.0505 (17)0.0407 (16)0.0540 (17)0.0059 (13)0.0190 (13)0.0018 (13)
C70.063 (2)0.067 (2)0.0506 (18)0.0077 (16)0.0274 (15)0.0083 (15)
C80.0560 (19)0.072 (2)0.060 (2)0.0090 (17)0.0216 (16)0.0223 (18)
C90.0556 (19)0.0517 (19)0.074 (2)0.0187 (15)0.0041 (16)0.0255 (17)
O30.0938 (16)0.0357 (11)0.0498 (12)0.0046 (10)0.0348 (11)0.0029 (9)
O40.1026 (17)0.0302 (11)0.0684 (14)0.0035 (11)0.0474 (12)0.0045 (10)
N30.0545 (15)0.0510 (15)0.0530 (14)0.0023 (12)0.0282 (11)0.0153 (12)
N40.0506 (14)0.0439 (14)0.0497 (14)0.0008 (11)0.0214 (11)0.0049 (11)
C100.070 (2)0.085 (3)0.0489 (18)0.0068 (19)0.0272 (16)0.0100 (17)
C110.0487 (16)0.0323 (15)0.0505 (16)0.0016 (12)0.0189 (13)0.0036 (12)
C120.0395 (15)0.0341 (14)0.0414 (14)0.0003 (12)0.0104 (11)0.0038 (12)
C130.0370 (14)0.0360 (15)0.0497 (16)0.0003 (12)0.0120 (12)0.0085 (12)
C140.0406 (15)0.0433 (16)0.0567 (18)0.0041 (13)0.0130 (13)0.0134 (14)
C150.0557 (19)0.050 (2)0.080 (2)0.0011 (15)0.0145 (16)0.0312 (18)
C160.065 (2)0.0334 (17)0.104 (3)0.0039 (15)0.000 (2)0.0169 (18)
C170.071 (2)0.0361 (18)0.094 (3)0.0008 (16)0.0151 (19)0.0054 (17)
C180.0606 (19)0.0383 (16)0.0621 (18)0.0027 (14)0.0183 (15)0.0017 (14)
Geometric parameters (Å, °) top
O1—C21.246 (3)O3—C111.267 (3)
O2—C21.280 (3)O3—H3A0.8200
O2—H2A0.8200O4—C111.272 (3)
N1—N21.340 (3)N3—N41.337 (3)
N1—C51.363 (4)N3—C141.359 (4)
N1—C11.446 (3)N3—C101.458 (3)
N2—C31.340 (3)N4—C121.331 (3)
C1—H1A0.9600C10—H10A0.9600
C1—H1B0.9600C10—H10B0.9600
C1—H1C0.9600C10—H10C0.9600
C2—C31.461 (4)C11—C121.447 (3)
C3—C41.411 (3)C12—C131.427 (4)
C4—C61.400 (4)C13—C141.395 (4)
C4—C51.411 (3)C13—C181.402 (4)
C5—C91.410 (4)C14—C151.409 (4)
C6—C71.361 (4)C15—C161.331 (5)
C6—H6A0.9300C15—H15A0.9300
C7—C81.409 (4)C16—C171.425 (5)
C7—H7A0.9300C16—H16A0.9300
C8—C91.353 (4)C17—C181.374 (4)
C8—H8A0.9300C17—H17A0.9300
C9—H9A0.9300C18—H18A0.9300
C2—O2—H2A109.5C11—O3—H3A109.5
N2—N1—C5112.2 (2)N4—N3—C14112.5 (2)
N2—N1—C1120.8 (3)N4—N3—C10119.8 (2)
C5—N1—C1127.0 (3)C14—N3—C10127.7 (2)
C3—N2—N1105.7 (2)C12—N4—N3105.8 (2)
N1—C1—H1A109.5N3—C10—H10A109.5
N1—C1—H1B109.5N3—C10—H10B109.5
H1A—C1—H1B109.5H10A—C10—H10B109.5
N1—C1—H1C109.5N3—C10—H10C109.5
H1A—C1—H1C109.5H10A—C10—H10C109.5
H1B—C1—H1C109.5H10B—C10—H10C109.5
O1—C2—O2123.5 (2)O3—C11—O4122.9 (2)
O1—C2—C3121.3 (2)O3—C11—C12117.7 (2)
O2—C2—C3115.1 (2)O4—C11—C12119.3 (2)
N2—C3—C4111.7 (2)N4—C12—C13111.2 (2)
N2—C3—C2119.6 (2)N4—C12—C11120.8 (2)
C4—C3—C2128.6 (2)C13—C12—C11128.0 (2)
C6—C4—C3137.0 (2)C14—C13—C18119.8 (2)
C6—C4—C5119.3 (2)C14—C13—C12103.7 (2)
C3—C4—C5103.7 (2)C18—C13—C12136.5 (3)
N1—C5—C9132.3 (3)N3—C14—C13106.8 (2)
N1—C5—C4106.6 (2)N3—C14—C15130.8 (3)
C9—C5—C4121.1 (3)C13—C14—C15122.3 (3)
C7—C6—C4118.6 (3)C16—C15—C14117.2 (3)
C7—C6—H6A120.7C16—C15—H15A121.4
C4—C6—H6A120.7C14—C15—H15A121.4
C6—C7—C8121.9 (3)C15—C16—C17121.8 (3)
C6—C7—H7A119.1C15—C16—H16A119.1
C8—C7—H7A119.1C17—C16—H16A119.1
C9—C8—C7121.0 (3)C18—C17—C16121.5 (3)
C9—C8—H8A119.5C18—C17—H17A119.2
C7—C8—H8A119.5C16—C17—H17A119.2
C8—C9—C5118.1 (3)C17—C18—C13117.3 (3)
C8—C9—H9A121.0C17—C18—H18A121.3
C5—C9—H9A121.0C13—C18—H18A121.3
C5—N1—N2—C31.9 (3)C14—N3—N4—C121.7 (3)
C1—N1—N2—C3179.4 (3)C10—N3—N4—C12177.1 (2)
N1—N2—C3—C42.2 (3)N3—N4—C12—C130.8 (3)
N1—N2—C3—C2179.6 (2)N3—N4—C12—C11179.9 (2)
O1—C2—C3—N24.2 (4)O3—C11—C12—N4175.5 (2)
O2—C2—C3—N2178.0 (2)O4—C11—C12—N42.5 (4)
O1—C2—C3—C4179.0 (3)O3—C11—C12—C135.5 (4)
O2—C2—C3—C41.1 (4)O4—C11—C12—C13176.5 (3)
N2—C3—C4—C6178.1 (3)N4—C12—C13—C140.4 (3)
C2—C3—C4—C61.0 (5)C11—C12—C13—C14178.7 (3)
N2—C3—C4—C51.6 (3)N4—C12—C13—C18178.5 (3)
C2—C3—C4—C5178.7 (3)C11—C12—C13—C180.6 (5)
N2—N1—C5—C9178.6 (3)N4—N3—C14—C132.0 (3)
C1—N1—C5—C91.4 (5)C10—N3—C14—C13176.7 (3)
N2—N1—C5—C41.0 (3)N4—N3—C14—C15179.1 (3)
C1—N1—C5—C4178.2 (3)C10—N3—C14—C150.4 (5)
C6—C4—C5—N1179.4 (2)C18—C13—C14—N3179.9 (2)
C3—C4—C5—N10.4 (3)C12—C13—C14—N31.4 (3)
C6—C4—C5—C90.3 (4)C18—C13—C14—C152.7 (4)
C3—C4—C5—C9179.9 (2)C12—C13—C14—C15178.8 (3)
C3—C4—C6—C7179.1 (3)N3—C14—C15—C16179.3 (3)
C5—C4—C6—C70.5 (4)C13—C14—C15—C162.6 (4)
C4—C6—C7—C81.2 (4)C14—C15—C16—C171.6 (5)
C6—C7—C8—C91.1 (5)C15—C16—C17—C180.9 (5)
C7—C8—C9—C50.3 (5)C16—C17—C18—C130.9 (5)
N1—C5—C9—C8179.2 (3)C14—C13—C18—C171.8 (4)
C4—C5—C9—C80.4 (4)C12—C13—C18—C17179.7 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O1i0.821.822.632 (3)173
O3—H3A···O4ii0.821.822.619 (3)164
C8—H8A···O1iii0.932.523.293 (4)140
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x+1/2, −y+1/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °)
top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O1i0.821.822.632 (3)173
O3—H3A···O4ii0.821.822.619 (3)164
C8—H8A···O1iii0.932.523.293 (4)140
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x+1/2, −y+1/2, z−1/2.
Acknowledgements top

no

references
References top

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Rousseau, V. & Lindwall, H. G. (1950). J. Am. Chem. Soc. 72, 3047–3051.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.