5-Nitro-1-(prop-2-en-1-yl)-1H-indazole

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

doi:10.1107/S2414314617010914

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 7| July 2017| x171091

https://doi.org/10.1107/S2414314617010914

Open

access

5-Nitro-1-(prop-2-en-1-yl)-1H-indazole

Mohammed Boulhaoua,^a ^* Abdelhanine Essaghouani,^a Sanae Lahmidi,^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 S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 16 June 2017; accepted 24 July 2017; online 28 July 2017)

In the crystal, the title molecule, C₁₀H₉N₃O₂, packs in layers approximately parallel to (100), which are formed by the association of zigzag chains constructed by weak C—H⋯O interactions. The allyl group is disordered over two positions, with a ratio of their occupancies close to 70:30.

Keywords: crystal structure; hydrogen bond; indazole.

CCDC reference: 1564302

Structure description

As a continuation of our research work on indazole derivatives (Boulhaoua et al., 2016 ), we have studied the action of allyl bromide towards 5-nitro-1H-indazole under phase-transfer catalysis conditions, by using tetra-n-butylammonium bromide (TBAB) as catalyst and potassium carbonate as base. This readily leads to the title compound (Fig. 1) in good yield.

Figure 1
The title molecule with labelling scheme and 50% probability ellipsoids. Only one orientation of the disordered allyl group is shown.

In the crystal, the molecule forms zigzag chains running parallel to the c axis through weak intermolecular C7—H7⋯O1ⁱ hydrogen bonds (Table 1 and Fig. 2). The chains pack so as to form layers approximately parallel to (100) aided by weak C9A—H9A⋯O1ⁱⁱ interactions (Table 1 and Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O1ⁱ	1.00 (2)	2.56 (3)	3.552 (3)	168 (2)
C9A—H9A⋯O1ⁱⁱ	0.93	2.55	3.404 (17)	154
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y, z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Figure 2
Packing viewed along the a axis with C—H⋯O interactions shown as dotted lines.

Figure 3
Packing viewed along the c axis with C—H⋯O interactions shown as dotted lines.

Synthesis and crystallization

To a solution of 5-nitro-1H-indazole (0.5 g, 3 mmol) in THF (25 ml) was added allyl bromide (0.26 ml, 3 mmol), potassium carbonate (0.83 g, 6 mmol) and a catalytic amount 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 resulting residue was purified by column chromatography (EtOAc/hexane, 2/8). The title compound was obtained as colourless crystals in 70% yield.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The allyl group is disordered over two partially resolved orientations for which occupancies converged toward 0.702 (12) and 0.298 (12). The two components of the disorder were refined subject to restraints that their geometries be comparable (SADI command in SHELXL; Sheldrick, 2015b ) and pairs of C atoms were constrained to have identical displacement parameters (EADP command in SHELXL; Sheldrick, 2015b). The absolute configuration could not be determined with certainty, and was thus assigned arbitrarily.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₉N₃O₂
M_r	203.20
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	6.9549 (5), 11.6778 (9), 12.2165 (9)
V (Å³)	992.20 (13)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.82
Crystal size (mm)	0.22 × 0.17 × 0.15

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.80, 0.89
No. of measured, independent and observed [I > 2σ(I)] reflections	7734, 1937, 1806
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.098, 1.05
No. of reflections	1937
No. of parameters	164
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.12
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1564302

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617010914/bh4025sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617010914/bh4025Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617010914/bh4025Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314617010914/bh4025Isup4.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 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

5-Nitro-1-(prop-2-en-1-yl)-1H-indazole top

Crystal data top

C₁₀H₉N₃O₂	D_x = 1.360 Mg m⁻³
M_r = 203.20	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 6584 reflections
a = 6.9549 (5) Å	θ = 3.8–72.3°
b = 11.6778 (9) Å	µ = 0.82 mm⁻¹
c = 12.2165 (9) Å	T = 298 K
V = 992.20 (13) Å³	Block, colourless
Z = 4	0.22 × 0.17 × 0.15 mm
F(000) = 424

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	1937 independent reflections
Radiation source: INCOATEC IµS micro-focus source	1806 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.030
Detector resolution: 10.4167 pixels mm^-1	θ_max = 72.3°, θ_min = 5.2°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −14→14
T_min = 0.80, T_max = 0.89	l = −13→14
7734 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0632P)² + 0.0423P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.003
1937 reflections	Δρ_max = 0.13 e Å⁻³
164 parameters	Δρ_min = −0.12 e Å⁻³
4 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
3 constraints	Extinction coefficient: 0.013 (2)
Primary atom site location: structure-invariant direct methods

Special details top

Refinement. The H-atoms of the disordered allyl group were placed in calculated positions (C—H = 0.93–0.97 Å) while the remainder were refined independently.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.7579 (3)	−0.04269 (14)	0.31969 (17)	0.0971 (7)
O2	0.7999 (4)	0.05941 (18)	0.17506 (16)	0.1030 (6)
N1	0.8126 (3)	0.42834 (13)	0.54140 (14)	0.0615 (4)
N2	0.8021 (3)	0.37982 (15)	0.64367 (15)	0.0675 (5)
N3	0.7819 (3)	0.04995 (16)	0.27451 (17)	0.0733 (5)
C1	0.7894 (2)	0.24152 (15)	0.51404 (15)	0.0532 (4)
C2	0.7815 (3)	0.14109 (14)	0.45294 (16)	0.0554 (4)
H2	0.775 (3)	0.068 (2)	0.487 (2)	0.066 (6)*
C3	0.7888 (3)	0.15275 (16)	0.34145 (17)	0.0590 (5)
C4	0.8024 (3)	0.25941 (17)	0.28784 (18)	0.0641 (5)
H4	0.812 (4)	0.263 (2)	0.212 (2)	0.079 (7)*
C5	0.8087 (3)	0.35883 (16)	0.34732 (17)	0.0629 (5)
H5	0.819 (4)	0.433 (2)	0.313 (2)	0.074 (6)*
C6	0.8037 (3)	0.34871 (14)	0.46140 (15)	0.0544 (4)
C7	0.7889 (3)	0.26889 (17)	0.62715 (18)	0.0631 (5)
H7	0.779 (4)	0.214 (2)	0.690 (2)	0.074 (7)*
C8	0.8333 (11)	0.5528 (2)	0.5382 (7)	0.0642 (15)	0.702 (12)
H8A	0.942664	0.572027	0.492453	0.077*	0.702 (12)
H8B	0.860253	0.580262	0.611529	0.077*	0.702 (12)
C9	0.6597 (12)	0.6133 (10)	0.4954 (7)	0.0727 (11)	0.702 (12)
H9	0.541851	0.598228	0.528387	0.087*	0.702 (12)
C10	0.6638 (13)	0.6853 (5)	0.4153 (5)	0.1027 (18)	0.702 (12)
H10A	0.779679	0.702051	0.380736	0.123*	0.702 (12)
H10B	0.551014	0.720502	0.392042	0.123*	0.702 (12)
C8A	0.841 (3)	0.5494 (5)	0.516 (2)	0.0642 (15)	0.298 (12)
H8AA	0.898139	0.558371	0.443829	0.077*	0.298 (12)
H8AB	0.924583	0.585220	0.569494	0.077*	0.298 (12)
C9A	0.645 (3)	0.601 (3)	0.5191 (18)	0.0727 (11)	0.298 (12)
H9A	0.570403	0.588830	0.581261	0.087*	0.298 (12)
C10A	0.572 (3)	0.6615 (13)	0.4409 (14)	0.1027 (18)	0.298 (12)
H10C	0.643556	0.675116	0.377733	0.123*	0.298 (12)
H10D	0.449119	0.691462	0.447651	0.123*	0.298 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1346 (18)	0.0541 (8)	0.1026 (13)	0.0013 (10)	0.0014 (12)	−0.0084 (8)
O2	0.1418 (17)	0.0913 (12)	0.0761 (12)	0.0089 (13)	0.0128 (12)	−0.0165 (9)
N1	0.0684 (9)	0.0501 (8)	0.0660 (9)	−0.0022 (7)	−0.0033 (8)	0.0038 (7)
N2	0.0756 (10)	0.0653 (9)	0.0617 (9)	−0.0027 (9)	−0.0005 (8)	0.0062 (7)
N3	0.0759 (11)	0.0638 (10)	0.0803 (12)	0.0082 (9)	0.0040 (10)	−0.0082 (8)
C1	0.0464 (8)	0.0517 (8)	0.0616 (10)	−0.0013 (7)	0.0005 (7)	0.0099 (7)
C2	0.0509 (9)	0.0475 (8)	0.0678 (11)	0.0026 (7)	0.0023 (8)	0.0097 (7)
C3	0.0562 (9)	0.0524 (9)	0.0684 (12)	0.0027 (8)	0.0010 (8)	0.0003 (7)
C4	0.0703 (11)	0.0632 (11)	0.0587 (11)	0.0015 (11)	0.0003 (9)	0.0084 (8)
C5	0.0720 (12)	0.0545 (9)	0.0624 (11)	−0.0032 (10)	−0.0012 (9)	0.0129 (8)
C6	0.0498 (8)	0.0500 (8)	0.0636 (10)	0.0009 (8)	−0.0021 (8)	0.0071 (7)
C7	0.0671 (11)	0.0590 (9)	0.0632 (11)	−0.0014 (9)	0.0022 (9)	0.0103 (8)
C8	0.0749 (14)	0.0489 (9)	0.069 (4)	−0.0057 (9)	0.002 (2)	−0.0027 (11)
C9	0.084 (2)	0.050 (3)	0.084 (4)	0.0044 (18)	−0.002 (2)	−0.001 (2)
C10	0.130 (5)	0.080 (3)	0.099 (4)	0.013 (3)	−0.020 (4)	0.016 (2)
C8A	0.0749 (14)	0.0489 (9)	0.069 (4)	−0.0057 (9)	0.002 (2)	−0.0027 (11)
C9A	0.084 (2)	0.050 (3)	0.084 (4)	0.0044 (18)	−0.002 (2)	−0.001 (2)
C10A	0.130 (5)	0.080 (3)	0.099 (4)	0.013 (3)	−0.020 (4)	0.016 (2)

Geometric parameters (Å, º) top

O1—N3	1.226 (3)	C5—H5	0.96 (3)
O2—N3	1.226 (3)	C7—H7	1.00 (2)
N1—C6	1.351 (3)	C8—C9	1.493 (4)
N1—N2	1.374 (3)	C8—H8A	0.9700
N1—C8	1.461 (3)	C8—H8B	0.9700
N1—C8A	1.461 (3)	C9—C10	1.291 (5)
N2—C7	1.314 (3)	C9—H9	0.9300
N3—C3	1.453 (3)	C10—H10A	0.9300
C1—C2	1.391 (3)	C10—H10B	0.9300
C1—C6	1.411 (2)	C8A—C9A	1.493 (5)
C1—C7	1.418 (3)	C8A—H8AA	0.9700
C2—C3	1.370 (3)	C8A—H8AB	0.9700
C2—H2	0.95 (2)	C9A—C10A	1.291 (6)
C3—C4	1.410 (3)	C9A—H9A	0.9300
C4—C5	1.370 (3)	C10A—H10C	0.9300
C4—H4	0.93 (3)	C10A—H10D	0.9300
C5—C6	1.399 (3)

C6—N1—N2	111.81 (15)	N2—C7—C1	111.81 (17)
C6—N1—C8	132.1 (4)	N2—C7—H7	120.9 (15)
N2—N1—C8	116.1 (4)	C1—C7—H7	127.2 (15)
C6—N1—C8A	121.2 (11)	N1—C8—C9	113.6 (6)
N2—N1—C8A	126.9 (11)	N1—C8—H8A	108.8
C7—N2—N1	105.70 (18)	C9—C8—H8A	108.8
O1—N3—O2	122.6 (2)	N1—C8—H8B	108.8
O1—N3—C3	118.70 (19)	C9—C8—H8B	108.8
O2—N3—C3	118.7 (2)	H8A—C8—H8B	107.7
C2—C1—C6	120.41 (17)	C10—C9—C8	123.7 (4)
C2—C1—C7	135.45 (17)	C10—C9—H9	118.1
C6—C1—C7	104.14 (16)	C8—C9—H9	118.1
C3—C2—C1	116.64 (16)	C9—C10—H10A	120.0
C3—C2—H2	121.9 (15)	C9—C10—H10B	120.0
C1—C2—H2	121.4 (15)	H10A—C10—H10B	120.0
C2—C3—C4	123.50 (19)	N1—C8A—C9A	105.1 (14)
C2—C3—N3	118.44 (17)	N1—C8A—H8AA	110.7
C4—C3—N3	118.06 (19)	C9A—C8A—H8AA	110.7
C5—C4—C3	120.27 (19)	N1—C8A—H8AB	110.7
C5—C4—H4	119.3 (16)	C9A—C8A—H8AB	110.7
C3—C4—H4	120.4 (17)	H8AA—C8A—H8AB	108.8
C4—C5—C6	117.12 (17)	C10A—C9A—C8A	123.9 (8)
C4—C5—H5	122.1 (15)	C10A—C9A—H9A	118.0
C6—C5—H5	120.8 (15)	C8A—C9A—H9A	118.0
N1—C6—C5	131.41 (17)	C9A—C10A—H10C	120.0
N1—C6—C1	106.52 (16)	C9A—C10A—H10D	120.0
C5—C6—C1	122.06 (17)	H10C—C10A—H10D	120.0

C6—N1—N2—C7	0.8 (2)	C8—N1—C6—C1	178.2 (4)
C8—N1—N2—C7	−178.5 (4)	C8A—N1—C6—C1	175.9 (9)
C8A—N1—N2—C7	−175.8 (9)	C4—C5—C6—N1	178.0 (2)
C6—C1—C2—C3	0.1 (2)	C4—C5—C6—C1	−1.0 (3)
C7—C1—C2—C3	−179.0 (2)	C2—C1—C6—N1	−178.67 (16)
C1—C2—C3—C4	−0.4 (3)	C7—C1—C6—N1	0.7 (2)
C1—C2—C3—N3	179.75 (16)	C2—C1—C6—C5	0.6 (3)
O1—N3—C3—C2	4.4 (3)	C7—C1—C6—C5	179.95 (18)
O2—N3—C3—C2	−175.7 (2)	N1—N2—C7—C1	−0.3 (3)
O1—N3—C3—C4	−175.5 (2)	C2—C1—C7—N2	179.0 (2)
O2—N3—C3—C4	4.5 (3)	C6—C1—C7—N2	−0.2 (2)
C2—C3—C4—C5	−0.1 (3)	C6—N1—C8—C9	70.0 (8)
N3—C3—C4—C5	179.8 (2)	N2—N1—C8—C9	−110.9 (6)
C3—C4—C5—C6	0.8 (3)	N1—C8—C9—C10	−126.0 (11)
N2—N1—C6—C5	179.9 (2)	C6—N1—C8A—C9A	98.4 (17)
C8—N1—C6—C5	−1.0 (5)	N2—N1—C8A—C9A	−85.3 (16)
C8A—N1—C6—C5	−3.3 (9)	N1—C8A—C9A—C10A	−128 (3)
N2—N1—C6—C1	−0.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	1.00 (2)	2.56 (3)	3.552 (3)	168 (2)
C9A—H9A···O1ⁱⁱ	0.93	2.55	3.404 (17)	154

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

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

Boulhaoua, M., El Hafi, M., Benchidmi, M., Essassi, E. M. & Mague, J. T. (2016). IUCrData, 1, x160480. Google Scholar
Brandenburg, K. & Putz, H. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2016). APEX3, SAINT and SADABS. Bruker AXS, Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 7| July 2017| x171091

https://doi.org/10.1107/S2414314617010914

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

5-Nitro-1-(prop-2-en-1-yl)-1H-indazole

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds