2-(3-Bromo-5-nitro-1H-indazol-1-yl)-1-phenyl­ethanone

Boulhaoua, M.; Benchidmi, M.; Essassi, E.M.; Saadi, M.; El Ammari, L.

doi:10.1107/S2414314617005594

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 4| April 2017| x170559

https://doi.org/10.1107/S2414314617005594

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2-(3-Bromo-5-nitro-1H-indazol-1-yl)-1-phenylethanone

Mohammed Boulhaoua,^a Mohammed Benchidmi,^a ^* El Mokhtar Essassi,^a Mohamed Saadi ^b and Lahcen El Ammari ^b

^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

Edited by P. Bombicz, Hungarian Academy of Sciences, Hungary (Received 28 March 2017; accepted 12 April 2017; online 18 April 2017)

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 crystal structure 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).

Figure 1
The molecular structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small circles of arbitrary radius.

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.

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
Three-dimensional view of the structure of the title compound, showing molecules linked together by hydrogen bonds (dashed blue lines) and π–π interactions (green line).

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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₀BrN₃O₃
M_r	360.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	13.2690 (6), 15.6721 (7), 7.2136 (3)
β (°)	99.029 (2)
V (Å³)	1481.50 (11)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.79
Crystal size (mm)	0.38 × 0.31 × 0.26

Data collection
Diffractometer	Bruker X8 APEX
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.547, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	36498, 3823, 2760
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.102, 1.05
No. of reflections	3823
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.41
Computer programs: APEX2 and SAINT-Plus (Bruker, 2009 ), SHELXTL2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1543758

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617005594/zp4013sup1.cif

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

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: 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).

2-(3-Bromo-5-nitro-1H-indazol-1-yl)-1-phenylethanone top

Crystal data top

C₁₅H₁₀BrN₃O₃	D_x = 1.615 Mg m⁻³
M_r = 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

Data collection top

Bruker X8 APEX diffractometer	3823 independent reflections
Radiation source: fine-focus sealed tube	2760 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
φ and ω scans	θ_max = 28.7°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −13→17
T_min = 0.547, T_max = 0.746	k = −21→21
36498 measured reflections	l = −9→9

Refinement top

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(F_o²) + (0.0497P)² + 0.5228P] where P = (F_o² + 2F_c²)/3
3823 reflections	(Δ/σ)_max = 0.001
199 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

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.

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

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

References

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