organic compounds
3-Chloro-1-ethyl-6-nitro-1H-indazole
aLaboratoire de Chimie Organique Hétérocyclique URAC 21, Pôle de Compétence Pharmacochimie, Av. Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco, and bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA
*Correspondence e-mail: dedah6211672@gmail.com
In the title compound, C9H8ClN3O2, the terminal C atom of the ethyl group deviates from the indazole ring (r.m.s. deviation = 0.008 Å) by 1.588 (3) Å. The dihedral angle between the ring system and the attached nitro group is 2.8 (3)°. In the crystal, weak C—H⋯O interactions link the molecules into zigzag chains propagating along [001]. In addition, weak π–π stacking interactions [centroid–centroid separations = 3.6809 (10) and 3.7393 (11) Å] help to consolidate the packing.
Keywords: crystal structure; hydrogen bond; indazole.
CCDC reference: 1559669
Structure description
As a continuation of our studies on indazole derivatives (Mohamed Abdelahi et al., 2017), we report here the synthesis and of the title compound, C9H8ClN3O2.
The molecular structure of the title compound is illustrated in Fig. 1. Apart from the terminal carbon atom (C9) of the ethyl moiety, it is essentially planar, as evident from the dihedral angle between the indazole ring plane and nitro group of 2.8 (3)°. Atom C9 deviates from the ring plane by 1.588 (3) Å.
In the crystal, a weak C4—H4⋯O2i interaction (Table 1) links the molecules into zigzag chains propagating along the c-axis direction (Fig. 2). In addition, weak π–π stacking interactions are observed [Cg1⋯Cg2ii = 3.6809 (10) Å, Cg2⋯Cg2ii = 3.7393 (11) Å, where Cg1 is the centroid of the N1/N2/C7/C2/C1 ring and Cg2 is the centroid of the C2–C7 ring; symmetry code: (ii) 2 − x, −y, 2 − z].
Synthesis and crystallization
To a solution of 6-nitro-1H-indazole (0.8 g, 5 mmol) in tetrahydrofuran (30 ml) were added bromoethane (0.8 g, 5 mmol), potassium carbonate (1.24 g, 9 mmol) and a catalytic quantity of tetra-n-butylammonium iodide. The mixture was stirred at room temperature for 48 h. The solution was filtered and the solvent removed under reduced pressure. The residue was recrystallized from ethanol solution to afford yellow plates of the title compound (yield: 68%).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1559669
https://doi.org/10.1107/S2414314617009725/hb4155sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617009725/hb4155Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617009725/hb4155Isup3.cdx
Supporting information file. DOI: https://doi.org/10.1107/S2414314617009725/hb4155Isup4.cml
Data collection: CrysAlis PRO (Rigaku OD, 2015); cell
CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C9H8ClN3O2 | F(000) = 464 |
Mr = 225.63 | Dx = 1.485 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
a = 7.4984 (3) Å | Cell parameters from 1252 reflections |
b = 16.2805 (7) Å | θ = 6.0–70.9° |
c = 8.3363 (3) Å | µ = 3.24 mm−1 |
β = 97.403 (4)° | T = 293 K |
V = 1009.19 (7) Å3 | Plate, yellow |
Z = 4 | 0.22 × 0.20 × 0.06 mm |
Rigaku Oxford diffraction diffractometer | 1916 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source | 1572 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
Detector resolution: 16.0416 pixels mm-1 | θmax = 71.4°, θmin = 5.4° |
ω scans | h = −7→9 |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015) | k = −19→16 |
Tmin = 0.493, Tmax = 1.000 | l = −9→10 |
3567 measured reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.0591P)2 + 0.080P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
1916 reflections | Δρmax = 0.20 e Å−3 |
137 parameters | Δρmin = −0.23 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. All the H atoms were placed in calculated positions and refined using the riding model with C—H bond lengths of 0.93 Å (CH), 0.97 Å (CH2) or 0.96 Å (CH3). Isotropic displacement parameters for these atoms were set to 1.2 (CH, CH2) or 1.5 (CH3) times Ueq of the parent atom. The methyl group was allowed to rotate, but not to tip, to best fit the electron density. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.34194 (8) | 0.57002 (5) | 0.22541 (6) | 0.0741 (2) | |
O1 | 0.0801 (2) | 0.38775 (13) | 1.0161 (2) | 0.0801 (5) | |
O2 | 0.0722 (3) | 0.28363 (12) | 0.8569 (3) | 0.1041 (8) | |
N1 | 0.3183 (2) | 0.63770 (11) | 0.5077 (2) | 0.0555 (4) | |
N2 | 0.2742 (2) | 0.61772 (10) | 0.6560 (2) | 0.0506 (4) | |
N3 | 0.0963 (2) | 0.35657 (12) | 0.8854 (3) | 0.0628 (5) | |
C1 | 0.2999 (2) | 0.57001 (14) | 0.4224 (2) | 0.0516 (4) | |
C2 | 0.2448 (2) | 0.50247 (12) | 0.5101 (2) | 0.0453 (4) | |
C3 | 0.2059 (2) | 0.41950 (13) | 0.4800 (3) | 0.0528 (5) | |
H3 | 0.2124 | 0.3969 | 0.3785 | 0.063* | |
C4 | 0.1581 (3) | 0.37243 (12) | 0.6036 (3) | 0.0556 (5) | |
H4 | 0.1329 | 0.3169 | 0.5876 | 0.067* | |
C5 | 0.1473 (2) | 0.40879 (12) | 0.7548 (2) | 0.0487 (4) | |
C6 | 0.1812 (2) | 0.48984 (12) | 0.7903 (2) | 0.0459 (4) | |
H6 | 0.1710 | 0.5121 | 0.8914 | 0.055* | |
C7 | 0.2320 (2) | 0.53656 (11) | 0.6633 (2) | 0.0432 (4) | |
C8 | 0.3023 (3) | 0.67764 (13) | 0.7875 (3) | 0.0585 (5) | |
H8A | 0.2237 | 0.6646 | 0.8677 | 0.070* | |
H8B | 0.2704 | 0.7319 | 0.7451 | 0.070* | |
C9 | 0.4930 (3) | 0.67852 (18) | 0.8667 (4) | 0.0791 (7) | |
H9A | 0.5700 | 0.6969 | 0.7905 | 0.119* | |
H9B | 0.5276 | 0.6241 | 0.9027 | 0.119* | |
H9C | 0.5038 | 0.7151 | 0.9577 | 0.119* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0669 (4) | 0.1084 (5) | 0.0482 (3) | 0.0074 (3) | 0.0124 (2) | 0.0114 (3) |
O1 | 0.0843 (12) | 0.0871 (13) | 0.0730 (11) | 0.0025 (10) | 0.0251 (9) | 0.0224 (10) |
O2 | 0.1397 (19) | 0.0585 (11) | 0.1091 (17) | −0.0275 (12) | −0.0026 (14) | 0.0253 (11) |
N1 | 0.0531 (9) | 0.0547 (9) | 0.0587 (9) | −0.0002 (7) | 0.0078 (7) | 0.0092 (8) |
N2 | 0.0570 (9) | 0.0410 (8) | 0.0542 (9) | −0.0021 (7) | 0.0091 (7) | −0.0008 (7) |
N3 | 0.0548 (10) | 0.0561 (10) | 0.0754 (13) | −0.0035 (8) | 0.0001 (8) | 0.0195 (9) |
C1 | 0.0413 (9) | 0.0646 (12) | 0.0490 (10) | 0.0044 (8) | 0.0054 (7) | 0.0071 (9) |
C2 | 0.0378 (8) | 0.0516 (10) | 0.0458 (9) | 0.0060 (7) | 0.0027 (7) | −0.0006 (8) |
C3 | 0.0488 (10) | 0.0549 (11) | 0.0536 (11) | 0.0079 (8) | 0.0028 (8) | −0.0130 (9) |
C4 | 0.0517 (10) | 0.0405 (9) | 0.0724 (13) | 0.0040 (8) | −0.0001 (9) | −0.0066 (9) |
C5 | 0.0408 (9) | 0.0456 (9) | 0.0583 (11) | 0.0028 (7) | 0.0015 (7) | 0.0064 (8) |
C6 | 0.0441 (9) | 0.0474 (9) | 0.0460 (9) | 0.0023 (7) | 0.0053 (7) | −0.0003 (7) |
C7 | 0.0384 (8) | 0.0418 (9) | 0.0487 (9) | 0.0020 (7) | 0.0030 (6) | −0.0022 (7) |
C8 | 0.0593 (12) | 0.0447 (10) | 0.0732 (13) | 0.0006 (9) | 0.0148 (9) | −0.0122 (9) |
C9 | 0.0680 (14) | 0.0823 (17) | 0.0850 (17) | −0.0009 (13) | 0.0020 (12) | −0.0333 (14) |
Cl1—C1 | 1.712 (2) | C3—C4 | 1.369 (3) |
O1—N3 | 1.222 (3) | C4—H4 | 0.9300 |
O2—N3 | 1.220 (3) | C4—C5 | 1.404 (3) |
N1—N2 | 1.360 (2) | C5—C6 | 1.369 (3) |
N1—C1 | 1.309 (3) | C6—H6 | 0.9300 |
N2—C7 | 1.362 (2) | C6—C7 | 1.396 (3) |
N2—C8 | 1.462 (3) | C8—H8A | 0.9700 |
N3—C5 | 1.470 (3) | C8—H8B | 0.9700 |
C1—C2 | 1.411 (3) | C8—C9 | 1.496 (3) |
C2—C3 | 1.398 (3) | C9—H9A | 0.9600 |
C2—C7 | 1.407 (2) | C9—H9B | 0.9600 |
C3—H3 | 0.9300 | C9—H9C | 0.9600 |
C1—N1—N2 | 105.75 (17) | C6—C5—N3 | 117.14 (18) |
N1—N2—C7 | 110.95 (16) | C6—C5—C4 | 124.74 (19) |
N1—N2—C8 | 119.57 (17) | C5—C6—H6 | 122.5 |
C7—N2—C8 | 128.75 (17) | C5—C6—C7 | 115.00 (17) |
O1—N3—C5 | 119.02 (19) | C7—C6—H6 | 122.5 |
O2—N3—O1 | 123.3 (2) | N2—C7—C2 | 107.41 (16) |
O2—N3—C5 | 117.7 (2) | N2—C7—C6 | 130.55 (17) |
N1—C1—Cl1 | 120.10 (17) | C6—C7—C2 | 122.03 (17) |
N1—C1—C2 | 113.08 (18) | N2—C8—H8A | 109.2 |
C2—C1—Cl1 | 126.83 (17) | N2—C8—H8B | 109.2 |
C3—C2—C1 | 136.70 (19) | N2—C8—C9 | 112.00 (18) |
C3—C2—C7 | 120.51 (18) | H8A—C8—H8B | 107.9 |
C7—C2—C1 | 102.79 (17) | C9—C8—H8A | 109.2 |
C2—C3—H3 | 120.8 | C9—C8—H8B | 109.2 |
C4—C3—C2 | 118.32 (18) | C8—C9—H9A | 109.5 |
C4—C3—H3 | 120.8 | C8—C9—H9B | 109.5 |
C3—C4—H4 | 120.3 | C8—C9—H9C | 109.5 |
C3—C4—C5 | 119.39 (18) | H9A—C9—H9B | 109.5 |
C5—C4—H4 | 120.3 | H9A—C9—H9C | 109.5 |
C4—C5—N3 | 118.12 (19) | H9B—C9—H9C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O2i | 0.93 | 2.52 | 3.280 (3) | 139 |
Symmetry code: (i) x, −y+1/2, z−1/2. |
Acknowledgements
JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.
References
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