organic compounds
5-Nitro-1-(prop-2-en-1-yl)-1H-indazole
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
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 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.
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).
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 (EtOAc/hexane, 2/8). The title compound was obtained as colourless crystals in 70% yield.
Refinement
Crystal data, data collection and structure . 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 could not be determined with certainty, and was thus assigned arbitrarily.
details are summarized in Table 2Structural data
CCDC reference: 1564302
https://doi.org/10.1107/S2414314617010914/bh4025sup1.cif
contains datablocks global, I. DOI: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
Data collection: APEX3 (Bruker, 2016); cell
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).C10H9N3O2 | Dx = 1.360 Mg m−3 |
Mr = 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 |
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 | Rint = 0.030 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 72.3°, θmin = 5.2° |
ω scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | k = −14→14 |
Tmin = 0.80, Tmax = 0.89 | l = −13→14 |
7734 measured reflections |
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(Fo2) + (0.0632P)2 + 0.0423P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.003 |
1937 reflections | Δρmax = 0.13 e Å−3 |
164 parameters | Δρmin = −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 |
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. |
x | y | z | Uiso*/Ueq | 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) |
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) |
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) |
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.