Crystal structure of N-(1-allyl-3-chloro-1H-indazol-5-yl)-4-methyl­benzene­sulfonamide

Hakima Chicha; El Mostapha Rakib; Mohamed Chigr; Mohamed Saadi; Lahcen El Ammari

doi:10.1107/S1600536814018194

. 2014 Aug 23;70(Pt 9):o1041–o1042. doi: 10.1107/S1600536814018194

Crystal structure of N-(1-allyl-3-chloro-1H-indazol-5-yl)-4-methylbenzenesulfonamide

Hakima Chicha ^a, El Mostapha Rakib ^a, Mohamed Chigr ^a,^*, Mohamed Saadi ^b, Lahcen El Ammari ^b

PMCID: PMC4186064 PMID: 25309215

Abstract

The 3-chloro-1H-indazole system in the title molecule, C₁₇H₁₆ClN₃O₂S, is almost planar, with the largest deviation from the mean plane being 0.029 (2) Å for one of the N atoms. This system is nearly perpendicular to the allyl chain, as indicated by the C—C—N—N torsion angle of −90.1 (6)° between them. The allyl group is split into two fragments, the major component has a site occupancy of 0.579 (7). The indazole system makes a dihedral angle of 47.53 (10)° with the plane through the benzene ring. In the crystal, molecules are connected by N—H⋯O and C—H⋯O hydrogen bonds, forming a three-dimensional network.

Keywords: crystal structure, benzenesulfonamides, biological activity, hydrogen bonding

Related literature

For the biological activity of sulfonamides, see: El-Sayed, et al. (2011 ▶); Mustafa et al. (2012 ▶); Scozzafava et al. (2003 ▶). For similar compounds, see: Abbassi et al. (2012 ▶, 2013 ▶); Chicha et al. (2014 ▶).

Experimental

Crystal data

C₁₇H₁₆ClN₃O₂S
M _r = 361.84
Orthorhombic,
a = 8.1736 (12) Å
b = 22.504 (4) Å
c = 19.279 (3) Å
V = 3546.2 (10) Å³
Z = 8
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 296 K
0.40 × 0.36 × 0.31 mm

Data collection

Bruker X8 APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ▶) T _min = 0.693, T _max = 0.747
18362 measured reflections
3621 independent reflections
2327 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.123
S = 1.02
3621 reflections
225 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814018194/tk5336sup1.cif

e-70-o1041-sup1.cif^{(25.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814018194/tk5336Isup2.hkl

e-70-o1041-Isup2.hkl^{(177.7KB, hkl)}

Click here for additional data file.^{(6.3KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814018194/tk5336Isup3.cml

Click here for additional data file.^{(1.4MB, tif)}

. DOI: 10.1107/S1600536814018194/tk5336fig1.tif

Molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.

Click here for additional data file.^{(1.4MB, tif)}

N . DOI: 10.1107/S1600536814018194/tk5336fig2.tif

Crystal structure of the title compound, showing molecules linked by N3–H3N⋯O1, C5–H5⋯O1 and C4–H4⋯O2 hydrogen bonds between molecules.

CCDC reference: 1018456

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯O1ⁱ	0.81	2.39	3.140 (3)	155
C4—H4⋯O2ⁱⁱ	0.93	2.44	3.364 (3)	171
C5—H5⋯O1ⁱ	0.93	2.58	3.282 (3)	132

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements, and the University Sultan Moulay Slimane, Beni-Mellal, Morocco, for financial support.

supplementary crystallographic information

S1. Chemical context

S2. Structural commentary

Sulfonamides are an important class of compounds which are widely used in the design of diverse classes of drug candidates (El-Sayed et al., 2011; Mustafa et al., 2012; Scozzafava et al., 2003). Previously, we identified a series of indazoles bearing a sulfonamide moiety with good antiproliferative activities (Abbassi et al., 2012; Abbassi, et al. 2013; Chicha et al., 2014).

The molecule of the title compound is built up from two fused five- and six-membered rings (N1 N2 C2 to C8) almost coplanar, with a maximum deviation of 0.029 (2) Å for N1 atom (Fig. 1). The dihedral angle between the indazol system and the plane through the benzene ring (C9 to C14) is of 47.53 (10)°. The allyl chain is perpendicular to the fused rings system as indicated by the C(16A)—C(15)—N(1)—N(2) torsion angle of -90.1 (6)°.

The cohesion of the crystal structure is ensured by N3–H3N···O1, C5–H5···O1 and C4–H4···O2 hydrogen bonds between molecules to form a three-dimensional network as shown in Fig. 2 and Table 1.

S3. Supramolecular features

S4. Database survey

S5. Synthesis and crystallization

A mixture of 1-allyl-3-chloro-5-nitroindazole (1.22 mmol) and anhydrous SnCl₂ (1.1 g, 6.1 mmol) in 25 ml of absolute ethanol was heated at 333 K for 6 h. After reduction, the starting material disappeared, and the solution was allowed to cool down. The pH was made slightly basic (pH 7–8) by addition of 5% aqueous potassium bicarbonate before extraction with ethyl acetate. The organic phase was washed with brine and dried over magnesium sulfate. The solvent was removed to afford the amine, which was immediately dissolved in pyridine (5 ml) and then reacted with 4-methylbenzenesulfonyl chloride (1.25 mmol) at room temperature for 24 h. After the reaction mixture was concentrated in vacuo, the resulting residue was purified by flash chromatography (eluted with ethyl acetate:hexane 2:8). The title compound was recrystallized from its ethanol solution. Yield: 65%, M.pt: 394 K.

S6. Refinement

The reflections (002), (110), (021) and (020), probably affected by the beam stop, were removed from the final refinement. The refinement of the model, i.e. disordered allyl group, required constraints on the distance C15—C16—C17 and atomic displacements of allyl group. The H atoms were located in a difference map and treated as riding with C—H = 0.96 Å, C—H = 0.97 Å, C—H = 0.93 Å, and N—H = 0.81 Å for methyl, methylene, aromatic CH and NH, respectively, and with U_iso(H) = 1.2 U_eq (methylene, aromatic, NH) and U_iso(H) = 1.5 U_eq for methyl.