organic compounds
3-Bromo-6-nitro-1-(prop-2-ynyl)-1H-indazole
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
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
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Refinement
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Data collection: APEX2 (Bruker, 2009); cell 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
https://doi.org/10.1107/S1600536811046927/xu5386sup1.cif
contains datablocks global, I. DOI: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
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
on silica gel with a hexane:ethyl acetate (9:1) solvent system. The compound was obtained as yellow crystals.Carbon-bound H-atoms were placed in calculated positions (C–H 0.93 Å) and were included in the
in the riding model approximation, with U(H) set to 1.2U(C). The acetylenic H-atom was located in a difference Fourier map and was refined. The 1 0 1 and -1 0 1 reflections were omitted owing to bad agreement.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
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–Hacetylene···Onitro hydrogen bond to generate a helical polymer running along the b-axis of the monoclinic (Fig. 2). Weak Br···Br contacts of 3.57 Å are present.For a related compound, 1-allyl-3-chloro-6-nitro-1H-indazole, see: El Brahmi et al. (2009).
Data collection: APEX2 (Bruker, 2009); cell
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).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. |
C10H6BrN3O2 | F(000) = 552 |
Mr = 280.09 | Dx = 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 |
Bruker APEX DUO diffractometer | 3137 independent reflections |
Radiation source: fine-focus sealed tube | 2236 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ω scans | θmax = 30.5°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −15→20 |
Tmin = 0.243, Tmax = 0.827 | k = −5→5 |
14908 measured reflections | l = −24→24 |
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(Fo2) + (0.0381P)2 + 0.4798P] where P = (Fo2 + 2Fc2)/3 |
3137 reflections | (Δ/σ)max = 0.001 |
149 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.76 e Å−3 |
C10H6BrN3O2 | V = 1039.78 (4) Å3 |
Mr = 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)° |
Bruker APEX DUO diffractometer | 3137 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2236 reflections with I > 2σ(I) |
Tmin = 0.243, Tmax = 0.827 | Rint = 0.023 |
14908 measured reflections |
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 | Δρmax = 0.52 e Å−3 |
3137 reflections | Δρmin = −0.76 e Å−3 |
149 parameters |
x | y | z | Uiso*/Ueq | ||
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)* |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.243, 0.827 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14908, 3137, 2236 |
Rint | 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 |
Δρmax, Δρmin (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).
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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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–Hacetylene···Onitro 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.