3-Chloro-1-ethyl-6-nitro-1H-indazole

Mohamed Abdelahi, M.M.; Sebbar, N.K.; Jasinski, J.P.; Kaur, M.; Essassi, E.M.; Benchidmi, M.

doi:10.1107/S2414314617009725

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 7| July 2017| x170972

https://doi.org/10.1107/S2414314617009725

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3-Chloro-1-ethyl-6-nitro-1H-indazole

Mohamed Mokhtar Mohamed Abdelahi,^a ^* Nada Kheira Sebbar,^a Jerry P. Jasinski,^b Manpreet Kaur,^b El Mokhtar Essassi ^a and Mohammed Benchidmi ^a

^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

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 17 June 2017; accepted 1 July 2017; online 13 July 2017)

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 crystal structure 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.

Figure 1
The molecular structure of the title compound, with atom labelling and 30% probability displacement ellipsoids.

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].

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
The packing viewed along the a-axis direction. Dashed lines indicate weak C—H⋯O interactions linking the molecules into [001] zigzag chains. H atoms not involved in the hydrogen bonds have been omitted for clarity.

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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₈ClN₃O₂
M_r	225.63
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.4984 (3), 16.2805 (7), 8.3363 (3)
β (°)	97.403 (4)
V (Å³)	1009.19 (7)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	3.24
Crystal size (mm)	0.22 × 0.20 × 0.06

Data collection
Diffractometer	Rigaku Oxford diffraction
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England.]$ )
T_min, T_max	0.493, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	3567, 1916, 1572
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.116, 1.03
No. of reflections	1916
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.23
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England.]$ ), SHELXT2014 (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1559669

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617009725/hb4155sup1.cif

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

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: 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).

3-Chloro-1-ethyl-6-nitro-1H-indazole top

Crystal data top

C₉H₈ClN₃O₂	F(000) = 464
M_r = 225.63	D_x = 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

Data collection top

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	R_int = 0.020
Detector resolution: 16.0416 pixels mm^-1	θ_max = 71.4°, θ_min = 5.4°
ω scans	h = −7→9
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −19→16
T_min = 0.493, T_max = 1.000	l = −9→10
3567 measured reflections

Refinement top

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(F_o²) + (0.0591P)² + 0.080P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
1916 reflections	Δρ_max = 0.20 e Å⁻³
137 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints

Special details top

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 U_eq of the parent atom. The methyl group was allowed to rotate, but not to tip, to best fit the electron density.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Mohamed Abdelahi, M. M., El Bakri, Y., Benchidmi, M., Essassi, E. M. & Mague, J. T. (2017). IUCrData, 2, x170432. Google Scholar
Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

IUCrDATA

ISSN: 2414-3146

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https://doi.org/10.1107/S2414314617009725

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3-Chloro-1-ethyl-6-nitro-1H-indazole

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds