Abstract
The molecule of the title compound, C8H6ClN3O2, is built up from fused five- and six-membered rings connected to a chlorine atom and to nitro and methyl groups. The indazole system is essentially planar with the largest deviation from the mean plane being 0.007 (2) Å. No classical hydrogen bonds are observed in the structure. Two molecules form a dimer organised by a symmetry centre via a close contact between a nitro-O atom and the chlorine atom [at 3.066 (2) Å this is shorter than the sum of their van der Waals radii].
Keywords: crystal structure, indazole derivative, Cl⋯O short contact
Related literature
For biological activities such as as antimicrobial, anticancer, antiinflammatory, antiplatelet and selective 5-HT6 antagonists of the title compound and derivatives, see: Schmidt et al. (2008 ▸); Shafakat Ali et al. (2012 ▸); Abbassi et al. (2014 ▸); Plescia et al. (2010 ▸); Lee et al. (2001 ▸); Liu et al. (2011 ▸).
Experimental
Crystal data
C8H6ClN3O2
M r = 211.61
Monoclinic,
a = 3.8273 (2) Å
b = 14.678 (6) Å
c = 15.549 (6) Å
β = 96.130 (9)°
V = 868.5 (6) Å3
Z = 4
Mo Kα radiation
μ = 0.41 mm−1
T = 296 K
0.31 × 0.27 × 0.21 mm
Data collection
Bruker X8 APEX Diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T min = 0.654, T max = 0.747
19793 measured reflections
2243 independent reflections
1963 reflections with I > 2σ(I)
R int = 0.028
Refinement
R[F 2 > 2σ(F 2)] = 0.043
wR(F 2) = 0.115
S = 1.10
2243 reflections
127 parameters
H-atom parameters constrained
Δρmax = 0.36 e Å−3
Δρmin = −0.27 e Å−3
Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 (Burnett & Johnson, 1996 ▸; Farrugia, 2012 ▸); software used to prepare material for publication: publCIF (Westrip, 2010 ▸).
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015018411/zp2019sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015018411/zp2019Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015018411/zp2019Isup3.cml
. DOI: 10.1107/S2056989015018411/zp2019fig1.tif
Plot of the molecule of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.
CCDC reference: 1429148
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements and the University Sultan Moulay Slimane, Beni-Mellal, Morocco, for financial support.
supplementary crystallographic information
S1. Comment
Indazole derivatives are a versatile class of compounds that have found use in biology, catalysis, and medicinal chemistry. They exhibit a variety of biological activities such as anti-microbial, anti-cancer, anti-inflammatory, anti- platelet, and selective 5-HT6 antagonists (Schmidt et al., 2008, Shafakat Ali et al., 2012, Abbassi et al., 2014, Plescia et al., 2010, Lee et al., 2001, Liu et al., 2011).
The two fused five- and six-membered rings (N2N3 C1 to C7) part of the molecule are almost planar, with a maximum deviation of -0.007 (2) Å at C1 atom (Fig.1). The chlorine atom and the nitro group linked to the indazole ring are nearly coplanar with the largest deviation from the mean plane being -0.070 (2) Å at O1. No classic hydrogen bonds are observed in the structure.
S2. Experimental
To a solution of 3-chloro-5-nitroindazole (6.13 mmol) in acetone (15 ml) was added potassium hydroxide (6.8 mmol). After 15 mn at 298 K, methyl iodide (12.26 mmol) was added dropwise. Upon disappearance of the starting material as indicated by TLC, the resulting mixture was evaporated. The crude material was dissolved with EtOAc (50 ml), washed with water and brine, dried over MgSO4 and the solvent was evaporated in vacuo. The resulting residue was purified by column chromatography (EtOAc/hexane 2/8). The title compound was recrystallized from ethanol at room temperature giving colourless crystals (m.p. 471 K, yield: 70%).
S3. Refinement
H atoms were located in a difference map and treated as riding with C–H = 0.96 Å and C–H = 0.93 Å for methyl and aromatic, respectively. All hydrogen with Uiso(H) = 1.5 Ueq for methyl and Uiso(H) = 1.2 Ueq for aromatic.
Figures
Fig. 1.
Plot of the molecule of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.
Crystal data
| C8H6ClN3O2 | Dx = 1.618 Mg m−3 |
| Mr = 211.61 | Melting point: 471 K |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| a = 3.8273 (2) Å | Cell parameters from 2243 reflections |
| b = 14.678 (6) Å | θ = 2.6–28.7° |
| c = 15.549 (6) Å | µ = 0.41 mm−1 |
| β = 96.130 (9)° | T = 296 K |
| V = 868.5 (6) Å3 | Block, colourless |
| Z = 4 | 0.31 × 0.27 × 0.21 mm |
| F(000) = 432 |
Data collection
| Bruker X8 APEX Diffractometer | 2243 independent reflections |
| Radiation source: fine-focus sealed tube | 1963 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.028 |
| φ and ω scans | θmax = 28.7°, θmin = 2.6° |
| Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −5→5 |
| Tmin = 0.654, Tmax = 0.747 | k = −19→19 |
| 19793 measured reflections | l = −20→20 |
Refinement
| Refinement on F2 | 0 restraints |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
| wR(F2) = 0.115 | w = 1/[σ2(Fo2) + (0.0484P)2 + 0.5276P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.10 | (Δ/σ)max < 0.001 |
| 2243 reflections | Δρmax = 0.36 e Å−3 |
| 127 parameters | Δρmin = −0.27 e Å−3 |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 0.39641 (14) | 0.41233 (3) | 0.10469 (3) | 0.04683 (17) | |
| N3 | 0.7340 (4) | 0.56202 (10) | 0.29223 (9) | 0.0345 (3) | |
| N2 | 0.6938 (4) | 0.48003 (10) | 0.25083 (10) | 0.0358 (3) | |
| N1 | 0.0460 (5) | 0.79442 (11) | 0.05310 (10) | 0.0416 (4) | |
| O2 | −0.0907 (5) | 0.75957 (11) | −0.01323 (11) | 0.0671 (5) | |
| O1 | 0.0360 (6) | 0.87596 (11) | 0.06625 (11) | 0.0669 (5) | |
| C3 | 0.4260 (4) | 0.59119 (11) | 0.16618 (10) | 0.0283 (3) | |
| C4 | 0.5778 (4) | 0.63052 (11) | 0.24420 (10) | 0.0299 (3) | |
| C2 | 0.2473 (4) | 0.64453 (11) | 0.10193 (10) | 0.0301 (3) | |
| H2 | 0.1459 | 0.6196 | 0.0502 | 0.036* | |
| C1 | 0.2289 (5) | 0.73599 (12) | 0.11912 (11) | 0.0325 (3) | |
| C7 | 0.5114 (4) | 0.49799 (12) | 0.17658 (11) | 0.0320 (3) | |
| C5 | 0.5521 (5) | 0.72408 (12) | 0.26022 (11) | 0.0373 (4) | |
| H5 | 0.6498 | 0.7497 | 0.3120 | 0.045* | |
| C6 | 0.3773 (5) | 0.77622 (12) | 0.19662 (12) | 0.0381 (4) | |
| H6 | 0.3564 | 0.8387 | 0.2047 | 0.046* | |
| C9 | 0.9194 (5) | 0.56629 (15) | 0.37845 (12) | 0.0442 (5) | |
| H9A | 1.0018 | 0.5066 | 0.3957 | 0.066* | |
| H9B | 1.1160 | 0.6069 | 0.3785 | 0.066* | |
| H9C | 0.7634 | 0.5882 | 0.4182 | 0.066* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0591 (3) | 0.0334 (2) | 0.0457 (3) | 0.00152 (19) | −0.0049 (2) | −0.01074 (18) |
| N3 | 0.0347 (8) | 0.0374 (8) | 0.0308 (7) | −0.0012 (6) | 0.0006 (6) | −0.0012 (6) |
| N2 | 0.0367 (8) | 0.0345 (7) | 0.0360 (7) | 0.0011 (6) | 0.0033 (6) | −0.0012 (6) |
| N1 | 0.0497 (9) | 0.0357 (8) | 0.0405 (8) | 0.0048 (7) | 0.0095 (7) | 0.0062 (6) |
| O2 | 0.0955 (14) | 0.0476 (9) | 0.0513 (9) | 0.0052 (9) | −0.0246 (9) | 0.0045 (7) |
| O1 | 0.1054 (15) | 0.0352 (8) | 0.0589 (10) | 0.0147 (9) | 0.0037 (9) | 0.0054 (7) |
| C3 | 0.0266 (8) | 0.0304 (8) | 0.0285 (7) | −0.0028 (6) | 0.0056 (6) | −0.0032 (6) |
| C4 | 0.0270 (8) | 0.0348 (8) | 0.0284 (7) | −0.0043 (6) | 0.0051 (6) | −0.0020 (6) |
| C2 | 0.0310 (8) | 0.0321 (8) | 0.0276 (7) | −0.0024 (6) | 0.0048 (6) | −0.0014 (6) |
| C1 | 0.0342 (9) | 0.0315 (8) | 0.0328 (8) | −0.0001 (7) | 0.0084 (7) | 0.0029 (6) |
| C7 | 0.0317 (8) | 0.0314 (8) | 0.0331 (8) | −0.0018 (6) | 0.0047 (6) | −0.0039 (6) |
| C5 | 0.0430 (10) | 0.0359 (9) | 0.0330 (8) | −0.0069 (7) | 0.0044 (7) | −0.0093 (7) |
| C6 | 0.0463 (10) | 0.0283 (8) | 0.0407 (9) | −0.0028 (7) | 0.0100 (8) | −0.0058 (7) |
| C9 | 0.0422 (10) | 0.0559 (12) | 0.0326 (9) | −0.0021 (9) | −0.0055 (8) | −0.0008 (8) |
Geometric parameters (Å, º)
| Cl1—C7 | 1.7086 (18) | C4—C5 | 1.401 (2) |
| N3—C4 | 1.353 (2) | C2—C1 | 1.372 (2) |
| N3—N2 | 1.366 (2) | C2—H2 | 0.9300 |
| N3—C9 | 1.450 (2) | C1—C6 | 1.406 (3) |
| N2—C7 | 1.311 (2) | C5—C6 | 1.367 (3) |
| N1—O1 | 1.215 (2) | C5—H5 | 0.9300 |
| N1—O2 | 1.218 (2) | C6—H6 | 0.9300 |
| N1—C1 | 1.458 (2) | C9—H9A | 0.9600 |
| C3—C2 | 1.390 (2) | C9—H9B | 0.9600 |
| C3—C4 | 1.411 (2) | C9—H9C | 0.9600 |
| C3—C7 | 1.412 (2) | ||
| C4—N3—N2 | 111.95 (14) | C2—C1—N1 | 117.97 (16) |
| C4—N3—C9 | 128.47 (16) | C6—C1—N1 | 118.43 (16) |
| N2—N3—C9 | 119.56 (16) | N2—C7—C3 | 113.01 (15) |
| C7—N2—N3 | 105.10 (14) | N2—C7—Cl1 | 120.27 (14) |
| O1—N1—O2 | 122.53 (18) | C3—C7—Cl1 | 126.72 (13) |
| O1—N1—C1 | 118.81 (17) | C6—C5—C4 | 117.27 (16) |
| O2—N1—C1 | 118.66 (16) | C6—C5—H5 | 121.4 |
| C2—C3—C4 | 120.87 (15) | C4—C5—H5 | 121.4 |
| C2—C3—C7 | 135.89 (15) | C5—C6—C1 | 120.43 (16) |
| C4—C3—C7 | 103.23 (14) | C5—C6—H6 | 119.8 |
| N3—C4—C5 | 131.73 (16) | C1—C6—H6 | 119.8 |
| N3—C4—C3 | 106.71 (15) | N3—C9—H9A | 109.5 |
| C5—C4—C3 | 121.56 (16) | N3—C9—H9B | 109.5 |
| C1—C2—C3 | 116.26 (15) | H9A—C9—H9B | 109.5 |
| C1—C2—H2 | 121.9 | N3—C9—H9C | 109.5 |
| C3—C2—H2 | 121.9 | H9A—C9—H9C | 109.5 |
| C2—C1—C6 | 123.60 (16) | H9B—C9—H9C | 109.5 |
Footnotes
Supporting information for this paper is available from the IUCr electronic archives (Reference: ZP2019).
References
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015018411/zp2019sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015018411/zp2019Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015018411/zp2019Isup3.cml
. DOI: 10.1107/S2056989015018411/zp2019fig1.tif
Plot of the molecule of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.
CCDC reference: 1429148
Additional supporting information: crystallographic information; 3D view; checkCIF report