organic compounds
2-(3-Bromo-5-nitro-1H-indazol-1-yl)-1-phenylethanone
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 bLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
*Correspondence e-mail: mohammed_benchidmi@yahoo.com
The 5-nitro-1H-indazol-1-yl moiety of the title compound, C15H10BrN3O3, is approximately planar, with the largest deviation from the mean plane being 0.079 (3) Å. The fused-ring system is virtually perpendicular to the mean plane through the 1-phenylethanone group, making a dihedral angle of 89.7 (2)°. In the crystal, pairs of molecules form inversion dimers via Br⋯O interactions [3.211 (2) Å]. The dimers are connected by C—H⋯O and C—H⋯N non-classical hydrogen bonds, in addition to π–π interactions [intercentroid distance = 3.6411 (12) Å], forming a three-dimensional network.
Keywords: crystal structure; 3-bromo-5-nitro-1H-indazole; phenylethanone; heterocyclic system; hydrogen bonding; π–π interactions; Br⋯O interactions.
CCDC reference: 1543758
Structure description
Recently, pharmacological tests have revealed that indazole derivatives present various biological activities, being potent anti-tumor (Abbassi et al., 2014); anti-microbial (Li et al., 2003); and anti-inflammatory (Schmidt et al., 2008) agents. The study of the title compound constitutes a continuation of our previous work on indazole derivatives (Boulhaoua et al., 2015; El Brahmi et al., 2012).
The molecule of the title compound is build up from fused five- and six-membered rings linked to a nitro group and to 1-phenylethanone group as shown in Fig. 1. The highly anisotropic ellipsoids of the phenyl ring are probably due to oscillation of this group. The fused ring system is approximately planar, with the largest deviation from the mean plane being 0.079 (3) Å at O2, and makes a dihedral angle of 89.7 (2)° with the mean plane through the 1-phenylethanone group (O3/C9–C15).
In the crystal, pairs of molecules form inversion dimers via Br1⋯O3 [3.211 (2) Å] interactions. The dimers are linked by C—H⋯O and C—H⋯N hydrogen bonds (Table 1) and by π–π interactions [intercentroid distance = 3.6411 (12) Å], forming a three dimensional structure as shown in Fig. 2.
Synthesis and crystallization
To a solution of 3-bromo-5-nitro-1H-indazole (0.5 g, 1.38 mmol) in DMF (15 ml) was added phenacyl bromide (0.27 g, 1.38 mmol), potassium carbonate (0.38 g, 2.76 mmol) and a catalytic quantity of tetra-n-butylammonium bromide. 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 methanol to afford the title compound as yellow crystals (yield: 65%; m.p. = 415 K).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1543758
https://doi.org/10.1107/S2414314617005594/zp4013sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617005594/zp4013Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617005594/zp4013Isup3.cml
Data collection: APEX2 (Bruker, 2009); cell
SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXTL2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).C15H10BrN3O3 | Dx = 1.615 Mg m−3 |
Mr = 360.17 | Melting point: 415 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.2690 (6) Å | Cell parameters from 3823 reflections |
b = 15.6721 (7) Å | θ = 2.6–28.7° |
c = 7.2136 (3) Å | µ = 2.79 mm−1 |
β = 99.029 (2)° | T = 296 K |
V = 1481.50 (11) Å3 | Block, yellow |
Z = 4 | 0.38 × 0.31 × 0.26 mm |
F(000) = 720 |
Bruker X8 APEX diffractometer | 3823 independent reflections |
Radiation source: fine-focus sealed tube | 2760 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
φ and ω scans | θmax = 28.7°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −13→17 |
Tmin = 0.547, Tmax = 0.746 | k = −21→21 |
36498 measured reflections | l = −9→9 |
Refinement on F2 | Primary atom site location: difference Fourier map |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0497P)2 + 0.5228P] where P = (Fo2 + 2Fc2)/3 |
3823 reflections | (Δ/σ)max = 0.001 |
199 parameters | Δρmax = 0.55 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.58530 (16) | 0.58951 (14) | 0.7404 (3) | 0.0394 (5) | |
C2 | 0.60236 (15) | 0.67859 (13) | 0.7387 (3) | 0.0344 (4) | |
C3 | 0.68138 (15) | 0.73149 (14) | 0.7045 (3) | 0.0372 (4) | |
H3 | 0.7425 | 0.7099 | 0.6763 | 0.045* | |
C4 | 0.66406 (15) | 0.81759 (15) | 0.7149 (3) | 0.0393 (5) | |
C5 | 0.57322 (17) | 0.85329 (14) | 0.7571 (3) | 0.0407 (5) | |
H5 | 0.5660 | 0.9123 | 0.7613 | 0.049* | |
C6 | 0.49523 (16) | 0.80152 (14) | 0.7922 (3) | 0.0383 (5) | |
H6 | 0.4346 | 0.8238 | 0.8212 | 0.046* | |
C7 | 0.51122 (14) | 0.71293 (14) | 0.7824 (3) | 0.0339 (4) | |
C8 | 0.34793 (17) | 0.64587 (16) | 0.8557 (3) | 0.0457 (5) | |
H8A | 0.3415 | 0.6932 | 0.9396 | 0.055* | |
H8B | 0.3376 | 0.5935 | 0.9220 | 0.055* | |
C9 | 0.26590 (16) | 0.65326 (14) | 0.6852 (3) | 0.0424 (5) | |
C10 | 0.15864 (17) | 0.64096 (17) | 0.7165 (4) | 0.0569 (7) | |
C11 | 0.1326 (2) | 0.6316 (3) | 0.8921 (5) | 0.0850 (10) | |
H11 | 0.1833 | 0.6344 | 0.9967 | 0.102* | |
C12 | 0.0327 (3) | 0.6182 (3) | 0.9170 (8) | 0.1154 (16) | |
H12 | 0.0160 | 0.6125 | 1.0369 | 0.138* | |
C13 | −0.0393 (3) | 0.6136 (4) | 0.7660 (11) | 0.139 (2) | |
H13 | −0.1065 | 0.6035 | 0.7820 | 0.167* | |
C14 | −0.0177 (3) | 0.6229 (5) | 0.5930 (11) | 0.187 (3) | |
H14 | −0.0698 | 0.6206 | 0.4905 | 0.225* | |
C15 | 0.0850 (3) | 0.6367 (4) | 0.5643 (7) | 0.1321 (19) | |
H15 | 0.1010 | 0.6425 | 0.4439 | 0.158* | |
N1 | 0.74533 (16) | 0.87569 (14) | 0.6780 (3) | 0.0524 (5) | |
N2 | 0.49530 (14) | 0.56952 (12) | 0.7801 (3) | 0.0442 (4) | |
N3 | 0.44972 (13) | 0.64583 (12) | 0.8077 (3) | 0.0406 (4) | |
O1 | 0.73418 (17) | 0.95111 (13) | 0.6986 (4) | 0.0893 (7) | |
O2 | 0.82021 (17) | 0.84566 (15) | 0.6268 (4) | 0.0855 (7) | |
O3 | 0.28825 (13) | 0.66909 (13) | 0.5328 (3) | 0.0609 (5) | |
Br1 | 0.67373 (2) | 0.50413 (2) | 0.68364 (4) | 0.05714 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0357 (11) | 0.0396 (11) | 0.0430 (12) | 0.0034 (9) | 0.0066 (9) | 0.0003 (9) |
C2 | 0.0313 (10) | 0.0390 (10) | 0.0328 (10) | −0.0007 (8) | 0.0047 (8) | 0.0004 (8) |
C3 | 0.0302 (10) | 0.0454 (11) | 0.0365 (11) | 0.0004 (8) | 0.0065 (8) | 0.0003 (9) |
C4 | 0.0357 (11) | 0.0434 (12) | 0.0389 (12) | −0.0082 (9) | 0.0062 (9) | 0.0030 (9) |
C5 | 0.0427 (12) | 0.0375 (11) | 0.0412 (12) | 0.0004 (9) | 0.0045 (9) | −0.0010 (9) |
C6 | 0.0336 (10) | 0.0444 (11) | 0.0377 (12) | 0.0025 (9) | 0.0078 (9) | −0.0023 (9) |
C7 | 0.0292 (9) | 0.0409 (11) | 0.0317 (10) | −0.0026 (8) | 0.0047 (8) | −0.0001 (8) |
C8 | 0.0364 (11) | 0.0502 (13) | 0.0536 (14) | −0.0052 (9) | 0.0169 (10) | −0.0009 (10) |
C9 | 0.0358 (11) | 0.0364 (11) | 0.0567 (14) | 0.0013 (9) | 0.0123 (10) | 0.0001 (10) |
C10 | 0.0331 (12) | 0.0498 (14) | 0.089 (2) | 0.0041 (10) | 0.0141 (12) | 0.0091 (13) |
C11 | 0.0444 (16) | 0.116 (3) | 0.102 (3) | 0.0016 (17) | 0.0338 (17) | 0.014 (2) |
C12 | 0.055 (2) | 0.144 (4) | 0.158 (4) | 0.005 (2) | 0.052 (3) | 0.032 (3) |
C13 | 0.043 (2) | 0.164 (5) | 0.213 (6) | 0.000 (2) | 0.031 (3) | 0.046 (4) |
C14 | 0.045 (2) | 0.344 (11) | 0.163 (6) | −0.003 (4) | −0.016 (3) | 0.048 (7) |
C15 | 0.0454 (19) | 0.233 (6) | 0.112 (3) | −0.008 (3) | −0.006 (2) | 0.034 (4) |
N1 | 0.0450 (12) | 0.0539 (13) | 0.0596 (13) | −0.0143 (10) | 0.0119 (10) | 0.0035 (10) |
N2 | 0.0395 (10) | 0.0397 (10) | 0.0541 (12) | −0.0036 (8) | 0.0099 (8) | −0.0005 (8) |
N3 | 0.0315 (9) | 0.0421 (10) | 0.0499 (11) | −0.0028 (7) | 0.0114 (8) | −0.0003 (8) |
O1 | 0.0766 (14) | 0.0484 (12) | 0.150 (2) | −0.0197 (10) | 0.0394 (14) | 0.0016 (13) |
O2 | 0.0570 (12) | 0.0768 (14) | 0.134 (2) | −0.0170 (11) | 0.0492 (13) | −0.0045 (14) |
O3 | 0.0487 (10) | 0.0787 (13) | 0.0566 (11) | 0.0044 (9) | 0.0123 (8) | 0.0108 (9) |
Br1 | 0.05290 (17) | 0.04388 (16) | 0.0780 (2) | 0.00958 (10) | 0.02077 (14) | −0.00060 (12) |
C1—N2 | 1.309 (3) | C8—H8B | 0.9700 |
C1—C2 | 1.415 (3) | C9—O3 | 1.209 (3) |
C1—Br1 | 1.867 (2) | C9—C10 | 1.488 (3) |
C2—C3 | 1.389 (3) | C10—C15 | 1.352 (5) |
C2—C7 | 1.404 (3) | C10—C11 | 1.372 (4) |
C3—C4 | 1.373 (3) | C11—C12 | 1.381 (4) |
C3—H3 | 0.9300 | C11—H11 | 0.9300 |
C4—C5 | 1.405 (3) | C12—C13 | 1.333 (7) |
C4—N1 | 1.467 (3) | C12—H12 | 0.9300 |
C5—C6 | 1.369 (3) | C13—C14 | 1.332 (8) |
C5—H5 | 0.9300 | C13—H13 | 0.9300 |
C6—C7 | 1.408 (3) | C14—C15 | 1.427 (7) |
C6—H6 | 0.9300 | C14—H14 | 0.9300 |
C7—N3 | 1.361 (3) | C15—H15 | 0.9300 |
C8—N3 | 1.446 (3) | N1—O1 | 1.203 (3) |
C8—C9 | 1.513 (3) | N1—O2 | 1.208 (3) |
C8—H8A | 0.9700 | N2—N3 | 1.369 (3) |
N2—C1—C2 | 112.99 (18) | O3—C9—C8 | 120.5 (2) |
N2—C1—Br1 | 120.19 (16) | C10—C9—C8 | 116.7 (2) |
C2—C1—Br1 | 126.77 (16) | C15—C10—C11 | 119.3 (3) |
C3—C2—C7 | 120.79 (19) | C15—C10—C9 | 118.0 (3) |
C3—C2—C1 | 135.80 (19) | C11—C10—C9 | 122.6 (3) |
C7—C2—C1 | 103.41 (17) | C10—C11—C12 | 121.5 (4) |
C4—C3—C2 | 116.08 (18) | C10—C11—H11 | 119.2 |
C4—C3—H3 | 122.0 | C12—C11—H11 | 119.2 |
C2—C3—H3 | 122.0 | C13—C12—C11 | 118.8 (4) |
C3—C4—C5 | 124.05 (19) | C13—C12—H12 | 120.6 |
C3—C4—N1 | 117.8 (2) | C11—C12—H12 | 120.6 |
C5—C4—N1 | 118.2 (2) | C14—C13—C12 | 121.8 (4) |
C6—C5—C4 | 120.2 (2) | C14—C13—H13 | 119.1 |
C6—C5—H5 | 119.9 | C12—C13—H13 | 119.1 |
C4—C5—H5 | 119.9 | C13—C14—C15 | 120.2 (5) |
C5—C6—C7 | 116.8 (2) | C13—C14—H14 | 119.9 |
C5—C6—H6 | 121.6 | C15—C14—H14 | 119.9 |
C7—C6—H6 | 121.6 | C10—C15—C14 | 118.3 (5) |
N3—C7—C2 | 106.83 (18) | C10—C15—H15 | 120.8 |
N3—C7—C6 | 131.08 (19) | C14—C15—H15 | 120.8 |
C2—C7—C6 | 122.09 (19) | O1—N1—O2 | 122.9 (2) |
N3—C8—C9 | 112.68 (19) | O1—N1—C4 | 118.6 (2) |
N3—C8—H8A | 109.1 | O2—N1—C4 | 118.5 (2) |
C9—C8—H8A | 109.1 | C1—N2—N3 | 105.19 (17) |
N3—C8—H8B | 109.1 | C7—N3—N2 | 111.57 (16) |
C9—C8—H8B | 109.1 | C7—N3—C8 | 129.35 (19) |
H8A—C8—H8B | 107.8 | N2—N3—C8 | 119.08 (18) |
O3—C9—C10 | 122.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8A···O3i | 0.97 | 2.40 | 3.315 (3) | 157 |
C8—H8B···O1ii | 0.97 | 2.53 | 3.244 (3) | 131 |
C5—H5···N2iii | 0.93 | 2.60 | 3.508 (3) | 166 |
C6—H6···O3i | 0.93 | 2.65 | 3.502 (3) | 152 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1, 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.
Funding information
Funding for this research was provided by: the University Mohammed V, Rabat, Morocco.
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