3-Bromo-6-nitro-1-(prop-2-yn­yl)-1H-indazole

El Brahmi, N.; Benchidmi, M.; Essassi, E.M.; Ladeira, S.; Ng, S.W.

doi:10.1107/S1600536811046927

organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3260

https://doi.org/10.1107/S1600536811046927

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3-Bromo-6-nitro-1-(prop-2-ynyl)-1H-indazole

Nabil El Brahmi,^a Mohamed Benchidmi,^a El Mokhtar Essassi,^a Sonia Ladeira ^b and Seik Weng Ng ^c,^d ^*

^aLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Université Mohammed V-Agdal, BP 1014 Avenue Ibn Batout, Rabat, Morocco, ^bLaboratoire de Chimie de Coordination, route de Narbonne, 31077 Toulouse, France, ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^dChemistry Department, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 5 November 2011; accepted 7 November 2011; online 12 November 2011)

In the title compound, C₁₀H₆BrN₃O₂, the indazole fused-ring system is nearly planar (r.m.s. deviation = 0.008 Å); its nitro substituent is nearly coplanar with the fused ring [dihedral angle = 4.5 (2)°]. In the crystal, adjacent molecules are linked by weak acetylene–nitro C—H⋯O hydrogen bonds, generating a helical chain running along the b axis.

Related literature

For a related compound, 1-allyl-3-chloro-6-nitro-1H-indazole, see: El Brahmi et al. (2009 ).

Experimental

Crystal data

C₁₀H₆BrN₃O₂
M_r = 280.09
Monoclinic, P 2₁ /n
a = 14.6573 (3) Å
b = 4.1650 (1) Å
c = 17.4566 (3) Å
β = 102.659 (1)°
V = 1039.78 (4) Å³
Z = 4
Mo Kα radiation
μ = 3.94 mm⁻¹
T = 295 K
0.50 × 0.10 × 0.05 mm

Data collection

Bruker APEX DUO diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.243, T_max = 0.827
14908 measured reflections
3137 independent reflections
2236 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.079
S = 1.03
3137 reflections
149 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H1⋯O1ⁱ	0.96 (3)	2.45 (3)	3.399 (3)	167 (3)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{3\over 2}}, -z+{\script{1\over 2}}]$ .

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: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811046927/xu5386sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811046927/xu5386Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811046927/xu5386Isup3.cml

checkCIF report

Comment top

We reported 1-allyl-3-chloro-6-nitro-1H-indazole, which exists as two independent molecules (El Brahmi et al., 2009). The present 1-propynyl-3-bromo-6-nitro-1H-indazole (Scheme I) also has halogen subsituent in the same position but the asymmetric unit consists of one molecule only. The indazole fused-ring is planar; its nitro substituent is nearly coplanar with the fused ring (Fig 1.). Adjacent molecules are linked by a C–H_acetylene···O_nitro hydrogen bond to generate a helical polymer running along the b-axis of the monoclinic unit cell (Fig. 2). Weak Br···Br contacts of 3.57 Å are present.

Related literature top

For a related compound, 1-allyl-3-chloro-6-nitro-1H-indazole, see: El Brahmi et al. (2009).

Experimental top

3-Bromo-6-nitroindazole (1.2 g, 5 mmol) and propargyl bromide (1.2 g, 10 mmol) were reacted in THF (40 ml) in the presence of potassium carbonate (1.4 g, 10 mmol) and tetra-n-butylammonium bromide (0.5 mmol). The mixture was stirred for 24 h, filtered, and the THF removed under vacuum. The product was separated by chromatography on silica gel with a hexane:ethyl acetate (9:1) solvent system. The compound was obtained as yellow crystals.

Structure description top

For a related compound, 1-allyl-3-chloro-6-nitro-1H-indazole, see: El Brahmi et al. (2009).

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: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₀H₆BrN₃O₂ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Helical chain motif.

3-Bromo-6-nitro-1-(prop-2-ynyl)-1H-indazole top

Crystal data top

C₁₀H₆BrN₃O₂	F(000) = 552
M_r = 280.09	D_x = 1.789 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5822 reflections
a = 14.6573 (3) Å	θ = 2.4–30.3°
b = 4.1650 (1) Å	µ = 3.94 mm⁻¹
c = 17.4566 (3) Å	T = 295 K
β = 102.659 (1)°	Plate, yellow
V = 1039.78 (4) Å³	0.50 × 0.10 × 0.05 mm
Z = 4

Data collection top

Bruker APEX DUO diffractometer	3137 independent reflections
Radiation source: fine-focus sealed tube	2236 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 30.5°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→20
T_min = 0.243, T_max = 0.827	k = −5→5
14908 measured reflections	l = −24→24

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0381P)² + 0.4798P] where P = (F_o² + 2F_c²)/3
3137 reflections	(Δ/σ)_max = 0.001
149 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.76 e Å⁻³

Crystal data top

C₁₀H₆BrN₃O₂	V = 1039.78 (4) Å³
M_r = 280.09	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 14.6573 (3) Å	µ = 3.94 mm⁻¹
b = 4.1650 (1) Å	T = 295 K
c = 17.4566 (3) Å	0.50 × 0.10 × 0.05 mm
β = 102.659 (1)°

Data collection top

Bruker APEX DUO diffractometer	3137 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2236 reflections with I > 2σ(I)
T_min = 0.243, T_max = 0.827	R_int = 0.023
14908 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.52 e Å⁻³
3137 reflections	Δρ_min = −0.76 e Å⁻³
149 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.234567 (17)	0.49344 (5)	0.664925 (11)	0.03944 (9)
O1	0.44171 (11)	−0.5183 (4)	0.38032 (10)	0.0431 (4)
O2	0.30475 (11)	−0.5312 (3)	0.30395 (9)	0.0401 (4)
N1	0.11630 (11)	0.3405 (4)	0.52285 (9)	0.0296 (3)
N2	0.11523 (10)	0.1781 (4)	0.45461 (9)	0.0262 (3)
N3	0.35862 (11)	−0.4437 (4)	0.36351 (10)	0.0278 (3)
C1	0.20201 (14)	0.3105 (4)	0.56494 (10)	0.0281 (4)
C2	0.26030 (13)	0.1289 (4)	0.52666 (10)	0.0250 (4)
C3	0.35342 (14)	0.0226 (4)	0.54510 (11)	0.0287 (4)
H3	0.3930	0.0758	0.5927	0.034*
C4	0.38431 (13)	−0.1624 (4)	0.49070 (11)	0.0278 (4)
H4	0.4456	−0.2367	0.5011	0.033*
C5	0.32278 (12)	−0.2386 (4)	0.41932 (10)	0.0237 (3)
C6	0.23102 (12)	−0.1400 (4)	0.39812 (10)	0.0231 (3)
H6	0.1923	−0.1923	0.3501	0.028*
C7	0.20061 (12)	0.0457 (4)	0.45476 (11)	0.0226 (3)
C8	0.02773 (13)	0.1524 (5)	0.39593 (11)	0.0288 (4)
H8A	−0.0229	0.2344	0.4179	0.035*
H8B	0.0150	−0.0722	0.3831	0.035*
C9	0.03026 (13)	0.3299 (5)	0.32386 (11)	0.0293 (4)
C10	0.03171 (17)	0.4760 (5)	0.26605 (13)	0.0403 (5)
H1	0.033 (2)	0.595 (7)	0.2189 (19)	0.069 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.06481 (17)	0.03278 (12)	0.02030 (10)	0.00030 (9)	0.00838 (9)	−0.00163 (7)
O1	0.0298 (8)	0.0620 (11)	0.0371 (8)	0.0170 (7)	0.0068 (6)	−0.0001 (7)
O2	0.0352 (8)	0.0498 (9)	0.0340 (8)	0.0039 (6)	0.0049 (6)	−0.0132 (6)
N1	0.0398 (9)	0.0261 (8)	0.0257 (8)	0.0012 (7)	0.0131 (7)	0.0006 (6)
N2	0.0266 (8)	0.0284 (8)	0.0244 (7)	0.0018 (6)	0.0072 (6)	−0.0018 (6)
N3	0.0270 (8)	0.0301 (8)	0.0269 (8)	0.0028 (6)	0.0071 (6)	0.0046 (6)
C1	0.0415 (11)	0.0236 (8)	0.0199 (8)	−0.0026 (7)	0.0084 (7)	0.0014 (6)
C2	0.0319 (10)	0.0205 (8)	0.0220 (8)	−0.0023 (7)	0.0045 (7)	0.0034 (6)
C3	0.0310 (10)	0.0299 (9)	0.0220 (8)	−0.0045 (7)	−0.0012 (7)	0.0030 (7)
C4	0.0227 (9)	0.0292 (9)	0.0292 (9)	0.0002 (7)	0.0008 (7)	0.0053 (7)
C5	0.0245 (9)	0.0228 (8)	0.0241 (8)	−0.0010 (6)	0.0057 (7)	0.0039 (6)
C6	0.0238 (9)	0.0232 (8)	0.0218 (8)	−0.0023 (7)	0.0036 (6)	0.0012 (6)
C7	0.0235 (8)	0.0204 (8)	0.0236 (8)	−0.0016 (6)	0.0044 (7)	0.0029 (6)
C8	0.0239 (9)	0.0292 (9)	0.0335 (10)	−0.0003 (7)	0.0062 (7)	−0.0008 (7)
C9	0.0246 (9)	0.0323 (10)	0.0298 (9)	−0.0007 (7)	0.0032 (7)	−0.0060 (7)
C10	0.0429 (12)	0.0481 (13)	0.0283 (10)	−0.0086 (10)	0.0042 (9)	−0.0021 (9)

Geometric parameters (Å, º) top

Br1—C1	1.8682 (17)	C3—H3	0.9300
O1—N3	1.228 (2)	C4—C5	1.405 (2)
O2—N3	1.216 (2)	C4—H4	0.9300
N1—C1	1.315 (2)	C5—C6	1.377 (2)
N1—N2	1.367 (2)	C6—C7	1.403 (2)
N2—C7	1.367 (2)	C6—H6	0.9300
N2—C8	1.459 (2)	C8—C9	1.467 (3)
N3—C5	1.476 (2)	C8—H8A	0.9700
C1—C2	1.414 (3)	C8—H8B	0.9700
C2—C7	1.407 (2)	C9—C10	1.183 (3)
C2—C3	1.403 (3)	C10—H1	0.96 (3)
C3—C4	1.374 (3)

C1—N1—N2	105.49 (15)	C5—C4—H4	120.2
N1—N2—C7	111.24 (15)	C6—C5—C4	124.76 (17)
N1—N2—C8	119.25 (15)	C6—C5—N3	117.59 (15)
C7—N2—C8	129.42 (15)	C4—C5—N3	117.65 (16)
O2—N3—O1	123.55 (17)	C5—C6—C7	114.68 (16)
O2—N3—C5	118.66 (15)	C5—C6—H6	122.7
O1—N3—C5	117.79 (16)	C7—C6—H6	122.7
N1—C1—C2	112.90 (15)	N2—C7—C6	130.79 (16)
N1—C1—Br1	120.03 (14)	N2—C7—C2	106.99 (16)
C2—C1—Br1	127.07 (14)	C6—C7—C2	122.22 (16)
C7—C2—C3	120.67 (17)	N2—C8—C9	112.42 (15)
C7—C2—C1	103.38 (16)	N2—C8—H8A	109.1
C3—C2—C1	135.92 (17)	C9—C8—H8A	109.1
C4—C3—C2	118.00 (17)	N2—C8—H8B	109.1
C4—C3—H3	121.0	C9—C8—H8B	109.1
C2—C3—H3	121.0	H8A—C8—H8B	107.9
C3—C4—C5	119.66 (17)	C10—C9—C8	179.2 (2)
C3—C4—H4	120.2	C9—C10—H1	180 (2)

C1—N1—N2—C7	0.35 (19)	O1—N3—C5—C4	−4.7 (2)
C1—N1—N2—C8	177.07 (15)	C4—C5—C6—C7	−0.9 (3)
N2—N1—C1—C2	−0.1 (2)	N3—C5—C6—C7	178.09 (15)
N2—N1—C1—Br1	−179.08 (12)	N1—N2—C7—C6	179.58 (17)
N1—C1—C2—C7	−0.2 (2)	C8—N2—C7—C6	3.3 (3)
Br1—C1—C2—C7	178.71 (13)	N1—N2—C7—C2	−0.49 (19)
N1—C1—C2—C3	−178.39 (19)	C8—N2—C7—C2	−176.79 (17)
Br1—C1—C2—C3	0.5 (3)	C5—C6—C7—N2	−178.79 (17)
C7—C2—C3—C4	0.4 (3)	C5—C6—C7—C2	1.3 (2)
C1—C2—C3—C4	178.4 (2)	C3—C2—C7—N2	178.93 (16)
C2—C3—C4—C5	0.0 (3)	C1—C2—C7—N2	0.41 (18)
C3—C4—C5—C6	0.2 (3)	C3—C2—C7—C6	−1.1 (3)
C3—C4—C5—N3	−178.71 (16)	C1—C2—C7—C6	−179.65 (16)
O2—N3—C5—C6	−4.2 (2)	N1—N2—C8—C9	112.94 (18)
O1—N3—C5—C6	176.26 (16)	C7—N2—C8—C9	−71.0 (2)
O2—N3—C5—C4	174.85 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H1···O1ⁱ	0.96 (3)	2.45 (3)	3.399 (3)	167 (3)

Symmetry code: (i) −x+1/2, y+3/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₆BrN₃O₂
M_r	280.09
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	14.6573 (3), 4.1650 (1), 17.4566 (3)
β (°)	102.659 (1)
V (Å³)	1039.78 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.94
Crystal size (mm)	0.50 × 0.10 × 0.05

Data collection
Diffractometer	Bruker APEX DUO
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.243, 0.827
No. of measured, independent and observed [I > 2σ(I)] reflections	14908, 3137, 2236
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.713

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.079, 1.03
No. of reflections	3137
No. of parameters	149
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.76

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H1···O1ⁱ	0.96 (3)	2.45 (3)	3.399 (3)	167 (3)

Symmetry code: (i) −x+1/2, y+3/2, −z+1/2.

Acknowledgements

We thank Université MohammedV-Agdal and the University of Malaya for supporting this study.

References

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