1-Allyl-3-chloro-5-nitro-1H-indazole

Chicha, H.; Rakib, E.M.; Spinelli, D.; Saadi, M.; El Ammari, L.

doi:10.1107/S1600536813021995

organic compounds

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ISSN: 2056-9890

Volume 69| Part 9| September 2013| Page o1410

doi:10.1107/S1600536813021995

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1-Allyl-3-chloro-5-nitro-1H-indazole

Hakima Chicha,^a ^* El Mostapha Rakib,^a Domenico Spinelli,^b Mohamed Saadi ^c and Lahcen El Ammari ^c

^aLaboratoire de Chimie Organique et Analytique, Université Sultan Moulay Slimane, Faculté des Sciences et Techniques, Béni-Mellal, BP 523, Morocco, ^bDipartimento di Chimica 'G. Ciamician', Università degli Studi di Bologna, Via Selmi 2, I-40126 Bologna, Italy, and ^cLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP. 1014, Rabat, Morocco
^*Correspondence e-mail: hakima_chicha@yahoo.fr

(Received 5 August 2013; accepted 6 August 2013; online 10 August 2013)

In the title compound, C₁₀H₈ClN₃O₂, the indazole ring system makes a dihedral angle of 7.9 (3)° with the plane through the nitro group. The allyl group is rotated out of the plane of the indazole ring system [N—N—C—C torsion angle = 104.28 (19)°]. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming zigzag chains propagating along the b-axis direction.

Related literature

For the pharmacological activity of indazole derivatives, see: Baraldi et al. (2001 ); Rodgers et al. (1996 ); Li et al. (2003 ); Lin et al. (2008 ). For a similar compound, see: El Brahmi et al. (2012 ).

Experimental

Crystal data

C₁₀H₈ClN₃O₂
M_r = 237.64
Monoclinic, P 2₁ /c
a = 13.3025 (6) Å
b = 11.2505 (5) Å
c = 7.3092 (3) Å
β = 91.343 (2)°
V = 1093.59 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 296 K
0.41 × 0.34 × 0.22 mm

Data collection

Bruker X8 APEX diffractometer
Absorption correction: multi-scan (SADABS: Sheldrick, 2008 ) T_min = 0.654, T_max = 0.747
14430 measured reflections
3069 independent reflections
1852 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.136
S = 1.02
3069 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2ⁱ	0.93	2.46	3.274 (2)	146
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813021995/bt6927sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813021995/bt6927Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813021995/bt6927Isup3.cml

checkCIF report

Comment top

Indazole derivatives are an important class of heterocyclic pharmaceuticals because of their significant and broad spectrum of biological properties, including antitumor, anti-HIV, antimicrobial, anti-inflammatory, and contraceptive activities (Baraldi et al., 2001; Rodgers et al., 1996; Li et al., 2003; Lin et al., 2008). The present work is a contribution to the investigation of indazole derivatives (El Brahmi et al., 2012).

In the molecule of 1-allyl-3-chloro-5-nitro-1H-indazole, the dihedral angle between the indazole system and the plan through the atoms forming the nitro group is of 7.9 (3)° and it is nearly perpendicular to the allyl group as indicated by the dihedral angle of 80.8 (3)°.

In the crystal, the molecules are interconnected by C–H···O hydrogen bonds forming zigzag chains running along the b axis as shown in Fig. 2 and Table 2.

Related literature top

For the pharmacological activity of indazole derivatives, see: Baraldi et al. (2001); Rodgers et al. (1996); Li et al. (2003); Lin et al. (2008). For a similar compound, see: El Brahmi et al. (2012).

Experimental top

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, allyl bromide (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 3/7). The title compound was recrystallized from ethanol.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure 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.
	Fig. 2. Partial crystal packing for the title compound showing C–H···O hydrogen bonds as dashed lines, showing a zigzag chain running along the b axis.

1-Allyl-3-chloro-5-nitro-1H-indazole top

Crystal data top

C₁₀H₈ClN₃O₂	F(000) = 488
M_r = 237.64	D_x = 1.443 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3069 reflections
a = 13.3025 (6) Å	θ = 2.4–29.6°
b = 11.2505 (5) Å	µ = 0.34 mm⁻¹
c = 7.3092 (3) Å	T = 296 K
β = 91.343 (2)°	Block, colourless
V = 1093.59 (8) Å³	0.41 × 0.34 × 0.22 mm
Z = 4

Data collection top

Bruker X8 APEX diffractometer	3069 independent reflections
Radiation source: fine-focus sealed tube	1852 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ϕ and ω scans	θ_max = 29.6°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS: Sheldrick, 2008)	h = −18→18
T_min = 0.654, T_max = 0.747	k = −10→15
14430 measured reflections	l = −9→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.047	Hydrogen site location: difference Fourier map
wR(F²) = 0.136	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.069P)² + 0.0517P] where P = (F_o² + 2F_c²)/3
3069 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₀H₈ClN₃O₂	V = 1093.59 (8) Å³
M_r = 237.64	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.3025 (6) Å	µ = 0.34 mm⁻¹
b = 11.2505 (5) Å	T = 296 K
c = 7.3092 (3) Å	0.41 × 0.34 × 0.22 mm
β = 91.343 (2)°

Data collection top

Bruker X8 APEX diffractometer	3069 independent reflections
Absorption correction: multi-scan (SADABS: Sheldrick, 2008)	1852 reflections with I > 2σ(I)
T_min = 0.654, T_max = 0.747	R_int = 0.046
14430 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.02	Δρ_max = 0.27 e Å⁻³
3069 reflections	Δρ_min = −0.33 e Å⁻³
145 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.39644 (11)	0.25338 (16)	1.0420 (2)	0.0451 (4)
C2	0.29681 (11)	0.22952 (14)	0.97697 (19)	0.0415 (4)
C3	0.24119 (12)	0.12846 (15)	0.9339 (2)	0.0462 (4)
H3	0.2681	0.0525	0.9450	0.055*
C4	0.14423 (13)	0.14758 (16)	0.8741 (2)	0.0517 (4)
C5	0.10115 (12)	0.26115 (18)	0.8562 (2)	0.0549 (5)
H5	0.0346	0.2685	0.8160	0.066*
C6	0.15549 (13)	0.36043 (16)	0.8970 (2)	0.0508 (4)
H6	0.1278	0.4360	0.8848	0.061*
C7	0.25499 (12)	0.34380 (14)	0.9583 (2)	0.0428 (4)
C8	0.32262 (15)	0.55248 (16)	1.0068 (3)	0.0596 (5)
H8A	0.3794	0.5846	1.0763	0.071*
H8B	0.2616	0.5785	1.0650	0.071*
C9	0.32387 (17)	0.59986 (17)	0.8194 (3)	0.0666 (5)
H9	0.3814	0.5866	0.7526	0.080*
C10	0.2520 (2)	0.6582 (2)	0.7404 (5)	0.1088 (10)
H10A	0.1931	0.6734	0.8025	0.131*
H10B	0.2588	0.6852	0.6210	0.131*
N1	0.32739 (10)	0.42252 (13)	1.01153 (19)	0.0492 (4)
N2	0.41482 (10)	0.36715 (13)	1.06173 (19)	0.0503 (4)
N3	0.08324 (14)	0.04395 (18)	0.8226 (2)	0.0720 (5)
O1	0.12321 (14)	−0.05345 (16)	0.8167 (3)	0.0968 (6)
O2	−0.00516 (13)	0.06089 (18)	0.7844 (3)	0.1118 (7)
Cl1	0.48743 (3)	0.15046 (5)	1.08995 (7)	0.0677 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0412 (8)	0.0522 (10)	0.0417 (8)	0.0014 (7)	−0.0009 (6)	0.0049 (7)
C2	0.0419 (8)	0.0462 (9)	0.0364 (7)	−0.0014 (7)	0.0006 (6)	0.0022 (7)
C3	0.0520 (10)	0.0463 (9)	0.0404 (8)	−0.0039 (7)	0.0034 (7)	0.0008 (7)
C4	0.0497 (10)	0.0619 (12)	0.0435 (8)	−0.0181 (8)	0.0021 (7)	−0.0055 (8)
C5	0.0388 (9)	0.0757 (13)	0.0500 (10)	−0.0016 (9)	−0.0047 (7)	−0.0016 (9)
C6	0.0458 (9)	0.0567 (11)	0.0498 (9)	0.0071 (8)	−0.0024 (7)	0.0017 (8)
C7	0.0428 (8)	0.0458 (9)	0.0398 (8)	−0.0012 (7)	−0.0008 (6)	0.0017 (7)
C8	0.0678 (12)	0.0427 (10)	0.0679 (12)	−0.0045 (8)	−0.0037 (9)	−0.0069 (8)
C9	0.0795 (14)	0.0424 (11)	0.0778 (13)	−0.0081 (10)	−0.0029 (11)	0.0029 (10)
C10	0.139 (3)	0.0582 (14)	0.127 (2)	−0.0137 (14)	−0.056 (2)	0.0176 (14)
N1	0.0485 (8)	0.0440 (8)	0.0548 (8)	−0.0036 (6)	−0.0071 (6)	0.0020 (6)
N2	0.0438 (8)	0.0544 (9)	0.0523 (8)	−0.0044 (6)	−0.0057 (6)	0.0045 (7)
N3	0.0667 (11)	0.0798 (13)	0.0694 (11)	−0.0279 (10)	0.0027 (9)	−0.0118 (10)
O1	0.0979 (12)	0.0673 (11)	0.1254 (15)	−0.0298 (10)	0.0049 (11)	−0.0242 (10)
O2	0.0639 (10)	0.1174 (15)	0.1528 (18)	−0.0334 (10)	−0.0243 (10)	−0.0240 (12)
Cl1	0.0516 (3)	0.0709 (4)	0.0803 (4)	0.0142 (2)	−0.0084 (2)	0.0080 (2)

Geometric parameters (Å, º) top

C1—N2	1.310 (2)	C7—N1	1.359 (2)
C1—C2	1.423 (2)	C8—N1	1.464 (2)
C1—Cl1	1.7056 (17)	C8—C9	1.470 (3)
C2—C3	1.389 (2)	C8—H8A	0.9700
C2—C7	1.406 (2)	C8—H8B	0.9700
C3—C4	1.369 (2)	C9—C10	1.286 (3)
C3—H3	0.9300	C9—H9	0.9300
C4—C5	1.405 (3)	C10—H10A	0.9300
C4—N3	1.465 (2)	C10—H10B	0.9300
C5—C6	1.360 (2)	N1—N2	1.3621 (19)
C5—H5	0.9300	N3—O2	1.217 (2)
C6—C7	1.400 (2)	N3—O1	1.219 (2)
C6—H6	0.9300

N2—C1—C2	113.02 (14)	C6—C7—C2	121.48 (15)
N2—C1—Cl1	120.71 (12)	N1—C8—C9	112.52 (16)
C2—C1—Cl1	126.27 (14)	N1—C8—H8A	109.1
C3—C2—C7	121.26 (15)	C9—C8—H8A	109.1
C3—C2—C1	135.84 (16)	N1—C8—H8B	109.1
C7—C2—C1	102.90 (14)	C9—C8—H8B	109.1
C4—C3—C2	115.89 (16)	H8A—C8—H8B	107.8
C4—C3—H3	122.1	C10—C9—C8	125.4 (3)
C2—C3—H3	122.1	C10—C9—H9	117.3
C3—C4—C5	123.49 (16)	C8—C9—H9	117.3
C3—C4—N3	117.96 (18)	C9—C10—H10A	120.0
C5—C4—N3	118.54 (17)	C9—C10—H10B	120.0
C6—C5—C4	120.86 (16)	H10A—C10—H10B	120.0
C6—C5—H5	119.6	C7—N1—N2	111.97 (13)
C4—C5—H5	119.6	C7—N1—C8	127.90 (15)
C5—C6—C7	117.01 (16)	N2—N1—C8	119.96 (14)
C5—C6—H6	121.5	C1—N2—N1	105.13 (13)
C7—C6—H6	121.5	O2—N3—O1	123.54 (19)
N1—C7—C6	131.54 (16)	O2—N3—C4	117.4 (2)
N1—C7—C2	106.97 (14)	O1—N3—C4	119.02 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ⁱ	0.93	2.46	3.274 (2)	146

Symmetry code: (i) −x, y+1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ⁱ	0.93	2.46	3.274 (2)	145.7

Symmetry code: (i) −x, y+1/2, −z+3/2.

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

References

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