1-(5-Nitro-1H-indazol-1-yl)ethanone

Boulhaoua, M.; Essaghouani, A.; Benchidmi, M.; Essassi, E.M.; Mague, J.T.

doi:10.1107/S2414314616009391

organic compounds

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Volume 1| Part 6| June 2016| x160939

doi:10.1107/S2414314616009391

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1-(5-Nitro-1H-indazol-1-yl)ethanone

Mohammed Boulhaoua,^a ^* Abdelhanine Essaghouani,^a Mohammed Benchidmi,^a El Mokhtar Essassi ^a and Joel T. Mague ^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 ^bDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: mboulhaoua@gmail.com

Edited by O. Blacque, University of Zürich, Switzerland (Received 25 May 2016; accepted 9 June 2016; online 14 June 2016)

In the title compound, C₉H₇N₃O₃, paired ribbons of molecules running in the a-axis direction are formed by intermolecular C—H⋯O and offset π-stacking interactions.

Keywords: crystal structure; indazole; π-stacking.

CCDC reference: 1484397

Structure description

Indazole derivatives are important structural fragments in medicinal chemistry having a broad spectrum of pharmacological activities including anti-inflammatory, anti-tumor, or HIV protease inhibition (Stefan et al., 2002 ; Arán et al., 2005 ; Boulouard et al., 2007 ) as well as exhibiting estrogen receptor (Steffan et al., 2004 ), antifungal and antibacterial activities (Tandon et al., 2005 ). Here we report the acetylation of 5-nitro-1H-indazole using acetic anhydride in the presence of a catalytic amount of acetic acid.

In the crystal structure of the title compound (Fig. 1), weak C3—H3⋯O1(1 + x, y, z) hydrogen bonds form ribbons parallel to (010) and running along the a-axis direction (Table 1 and Fig. 2). Two such chains are associated via offset π-stacking interactions between a six-membered ring in one chain and a five-membered ring in the other with a 3.7361 (9) Å separation (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1ⁱ	0.99 (2)	2.36 (2)	3.1816 (17)	140.0 (16)
Symmetry code: (i) x+1, y, z.

Figure 1
The title molecule with labeling scheme and 50% probability ellipsoids.

Figure 2
Packing viewed normal to (001). C—H⋯O interactions are shown by black dotted lines while a representative example of the offset π-stacking is shown by a purple dotted line.

Synthesis and crystallization

A mixture of 5-nitro-1H-indazole (0.6 g, 3.68 mmol), acetic acid (2 ml) and acetic anhydride (10 ml) were heated under reflux for 24 h, after completion of the reaction (monitored by TLC), the solvent was removed under vacuum. The residue obtained was recrystallized from ethanol to afford the title compound as colourless crystals (yield: 75%; m.p. 429–431 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₇N₃O₃
M_r	205.18
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	150
a, b, c (Å)	7.6004 (3), 7.9200 (3), 9.3621 (3)
α, β, γ (°)	113.020 (1), 91.404 (2), 118.350 (2)
V (Å³)	440.83 (3)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	1.02
Crystal size (mm)	0.27 × 0.21 × 0.04

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.84, 0.96
No. of measured, independent and observed [I > 2σ(I)] reflections	3385, 1641, 1456
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.105, 1.07
No. of reflections	1641
No. of parameters	165
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.22
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2014/7 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1484397

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616009391/zq4008sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616009391/zq4008Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616009391/zq4008Isup3.cdx

Supporting information file. DOI: 10.1107/S2414314616009391/zq4008Isup5.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

1-(5-Nitro-1H-indazol-1-yl)ethanone top

Crystal data top

C₉H₇N₃O₃	Z = 2
M_r = 205.18	F(000) = 212
Triclinic, P1	D_x = 1.546 Mg m⁻³
a = 7.6004 (3) Å	Cu Kα radiation, λ = 1.54178 Å
b = 7.9200 (3) Å	Cell parameters from 2667 reflections
c = 9.3621 (3) Å	θ = 5.3–72.3°
α = 113.020 (1)°	µ = 1.02 mm⁻¹
β = 91.404 (2)°	T = 150 K
γ = 118.350 (2)°	Thick plate, colourless
V = 440.83 (3) Å³	0.27 × 0.21 × 0.04 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	1641 independent reflections
Radiation source: INCOATEC IµS micro–focus source	1456 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.017
Detector resolution: 10.4167 pixels mm^-1	θ_max = 72.3°, θ_min = 5.3°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −9→9
T_min = 0.84, T_max = 0.96	l = −11→11
3385 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F² > 2σ(F²)] = 0.038	w = 1/[σ²(F_o²) + (0.0655P)² + 0.0862P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.105	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.30 e Å⁻³
1641 reflections	Δρ_min = −0.22 e Å⁻³
165 parameters	Extinction correction: SHELXL 2014/7 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.043 (5)

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
O1	0.31174 (15)	0.75516 (16)	0.38055 (12)	0.0335 (3)
O2	0.94598 (19)	0.7555 (2)	0.94836 (13)	0.0440 (3)
O3	1.17589 (18)	0.7624 (2)	0.81538 (15)	0.0462 (3)
N1	0.59744 (16)	0.74735 (18)	0.33098 (13)	0.0255 (3)
N2	0.71515 (18)	0.72440 (19)	0.22162 (13)	0.0290 (3)
N3	1.01405 (19)	0.75853 (19)	0.83144 (14)	0.0326 (3)
C1	0.8605 (2)	0.7163 (2)	0.28973 (16)	0.0286 (3)
H1	0.957 (3)	0.697 (3)	0.231 (2)	0.035 (4)*
C2	0.8463 (2)	0.7338 (2)	0.44671 (15)	0.0250 (3)
C3	0.9618 (2)	0.7351 (2)	0.56515 (16)	0.0270 (3)
H3	1.085 (3)	0.724 (3)	0.549 (2)	0.045 (5)*
C4	0.8964 (2)	0.7563 (2)	0.70377 (16)	0.0272 (3)
C5	0.7242 (2)	0.7752 (2)	0.72875 (16)	0.0285 (3)
H5	0.684 (3)	0.786 (3)	0.829 (2)	0.039 (5)*
C6	0.6096 (2)	0.7744 (2)	0.61171 (16)	0.0271 (3)
H6	0.485 (3)	0.784 (3)	0.6265 (19)	0.026 (4)*
C7	0.6741 (2)	0.75373 (19)	0.47014 (15)	0.0236 (3)
C8	0.4213 (2)	0.7508 (2)	0.28895 (16)	0.0268 (3)
C9	0.3841 (2)	0.7473 (3)	0.12989 (17)	0.0326 (4)
H9A	0.366 (3)	0.618 (3)	0.043 (2)	0.050 (5)*
H9B	0.499 (3)	0.865 (3)	0.126 (2)	0.040 (5)*
H9C	0.258 (3)	0.750 (3)	0.113 (2)	0.043 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0311 (5)	0.0428 (6)	0.0336 (5)	0.0228 (5)	0.0142 (4)	0.0190 (5)
O2	0.0520 (7)	0.0565 (7)	0.0307 (6)	0.0286 (6)	0.0132 (5)	0.0264 (5)
O3	0.0394 (6)	0.0649 (8)	0.0470 (7)	0.0302 (6)	0.0103 (5)	0.0335 (6)
N1	0.0258 (6)	0.0300 (6)	0.0226 (5)	0.0162 (5)	0.0090 (4)	0.0117 (4)
N2	0.0299 (6)	0.0354 (6)	0.0245 (6)	0.0193 (5)	0.0135 (5)	0.0133 (5)
N3	0.0335 (7)	0.0320 (6)	0.0296 (6)	0.0144 (5)	0.0047 (5)	0.0156 (5)
C1	0.0285 (7)	0.0352 (7)	0.0259 (6)	0.0195 (6)	0.0125 (5)	0.0139 (6)
C2	0.0248 (6)	0.0253 (6)	0.0245 (6)	0.0132 (5)	0.0086 (5)	0.0108 (5)
C3	0.0262 (6)	0.0263 (6)	0.0285 (7)	0.0137 (6)	0.0081 (5)	0.0128 (5)
C4	0.0292 (7)	0.0254 (6)	0.0243 (6)	0.0120 (6)	0.0054 (5)	0.0121 (5)
C5	0.0305 (7)	0.0271 (7)	0.0241 (6)	0.0127 (6)	0.0097 (5)	0.0114 (5)
C6	0.0272 (7)	0.0267 (6)	0.0257 (7)	0.0135 (6)	0.0105 (5)	0.0110 (5)
C7	0.0248 (6)	0.0221 (6)	0.0219 (6)	0.0115 (5)	0.0072 (5)	0.0092 (5)
C8	0.0243 (6)	0.0262 (6)	0.0280 (7)	0.0134 (6)	0.0065 (5)	0.0104 (5)
C9	0.0331 (7)	0.0410 (8)	0.0279 (7)	0.0217 (7)	0.0088 (6)	0.0166 (6)

Geometric parameters (Å, º) top

O1—C8	1.2119 (17)	C3—C4	1.3787 (18)
O2—N3	1.2259 (16)	C3—H3	0.99 (2)
O3—N3	1.2302 (18)	C4—C5	1.401 (2)
N1—C7	1.3866 (16)	C5—C6	1.379 (2)
N1—N2	1.3912 (15)	C5—H5	0.981 (18)
N1—C8	1.4020 (17)	C6—C7	1.4005 (17)
N2—C1	1.3018 (19)	C6—H6	0.994 (18)
N3—C4	1.4646 (17)	C8—C9	1.4959 (19)
C1—C2	1.4331 (18)	C9—H9A	0.97 (2)
C1—H1	0.962 (18)	C9—H9B	0.941 (19)
C2—C3	1.3915 (19)	C9—H9C	0.98 (2)
C2—C7	1.4032 (19)

C7—N1—N2	111.10 (10)	C6—C5—C4	120.29 (12)
C7—N1—C8	129.03 (11)	C6—C5—H5	120.1 (11)
N2—N1—C8	119.79 (11)	C4—C5—H5	119.6 (11)
C1—N2—N1	106.12 (11)	C5—C6—C7	116.86 (13)
O2—N3—O3	123.36 (13)	C5—C6—H6	121.2 (9)
O2—N3—C4	118.42 (12)	C7—C6—H6	121.9 (9)
O3—N3—C4	118.21 (12)	N1—C7—C6	132.17 (12)
N2—C1—C2	111.95 (12)	N1—C7—C2	105.71 (11)
N2—C1—H1	119.0 (11)	C6—C7—C2	122.12 (13)
C2—C1—H1	129.0 (11)	O1—C8—N1	119.14 (12)
C3—C2—C7	120.90 (12)	O1—C8—C9	125.17 (13)
C3—C2—C1	133.98 (13)	N1—C8—C9	115.70 (12)
C7—C2—C1	105.12 (12)	C8—C9—H9A	111.2 (12)
C4—C3—C2	116.08 (13)	C8—C9—H9B	110.3 (11)
C4—C3—H3	123.1 (12)	H9A—C9—H9B	106.8 (16)
C2—C3—H3	120.8 (12)	C8—C9—H9C	108.4 (11)
C3—C4—C5	123.74 (13)	H9A—C9—H9C	108.9 (16)
C3—C4—N3	117.76 (13)	H9B—C9—H9C	111.3 (16)
C5—C4—N3	118.51 (12)

C7—N1—N2—C1	0.09 (15)	C4—C5—C6—C7	0.1 (2)
C8—N1—N2—C1	−177.03 (12)	N2—N1—C7—C6	−179.93 (13)
N1—N2—C1—C2	−0.08 (16)	C8—N1—C7—C6	−3.1 (2)
N2—C1—C2—C3	−179.60 (14)	N2—N1—C7—C2	−0.06 (14)
N2—C1—C2—C7	0.05 (16)	C8—N1—C7—C2	176.72 (12)
C7—C2—C3—C4	0.16 (19)	C5—C6—C7—N1	−179.88 (13)
C1—C2—C3—C4	179.76 (14)	C5—C6—C7—C2	0.27 (19)
C2—C3—C4—C5	0.2 (2)	C3—C2—C7—N1	179.71 (11)
C2—C3—C4—N3	−179.96 (11)	C1—C2—C7—N1	0.01 (14)
O2—N3—C4—C3	−172.80 (12)	C3—C2—C7—C6	−0.4 (2)
O3—N3—C4—C3	6.87 (19)	C1—C2—C7—C6	179.89 (12)
O2—N3—C4—C5	7.06 (19)	C7—N1—C8—O1	−1.8 (2)
O3—N3—C4—C5	−173.27 (13)	N2—N1—C8—O1	174.72 (11)
C3—C4—C5—C6	−0.3 (2)	C7—N1—C8—C9	178.53 (12)
N3—C4—C5—C6	179.82 (11)	N2—N1—C8—C9	−4.93 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.99 (2)	2.36 (2)	3.1816 (17)	140.0 (16)

Symmetry code: (i) x+1, y, z.

Acknowledgements

The support of NSF–MRI Grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

References

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IUCrDATA

ISSN: 2414-3146

Volume 1| Part 6| June 2016| x160939

doi:10.1107/S2414314616009391

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

1-(5-Nitro-1H-indazol-1-yl)ethanone

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds