4-[(1,3-Dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-2-yl)meth­yl]-N′-[(E)-4-nitro­benzyl­idene]benzene­sulfono­hydrazide dimethyl sulfoxide monosolvate

Adailton J Bortoluzzi; Everton B Policarpi; Cristiano Mora; Kely N Oliveira; Ricardo J Nunes

doi:10.1107/S1600536811004697

. 2011 Feb 12;67(Pt 3):o627–o628. doi: 10.1107/S1600536811004697

4-[(1,3-Dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-2-yl)methyl]-N′-[(E)-4-nitrobenzylidene]benzenesulfonohydrazide dimethyl sulfoxide monosolvate

Adailton J Bortoluzzi ^a,^*, Everton B Policarpi ^a, Cristiano Mora ^a, Kely N Oliveira ^a, Ricardo J Nunes ^a

PMCID: PMC3051948 PMID: 21522382

Abstract

The molecular structure of the title compound, C₂₆H₁₈N₄O₆S·C₂H₆OS, shows an E conformation of the hydrazone double bond. The presence of a methylene group between the benzo[de]isoquinoline and benzenesulfonyl moieties allows the 4-nitrophenyl ring and the benzo[de]isoquinoline system to be parallel with respect to each other, so that the molecule adopts a U-shaped spatial conformation. The dihedral angle between mean planes of these aromatic groups is 4.4 (1)°. This special arrangement enables neighboring molecules to be intercalated, forming slipped π–π interactions [centroid–centroid distance = 3.535 (2) Å] between the 4-nitrophenyl and benzo[de]isoquinoline groups and point-to-face C—H⋯π interactions between the benzo[de]isoquinoline and benzenesulfonyl aromatic systems. In addition, the crystal packing also features an intermolecular N—H⋯O interaction involving the amine group and the dimethyl sulfoxide solvent molecule.

Related literature

For the therapeutic properties of sulfonylhydrazones, see: Rollas et al. (2002 ▶); Frlan et al. (2008 ▶); Lima et al. (1999 ▶); Sondhi et al. (2006 ▶) and for their biological activity, see: Kendall et al. (2007 ▶); Sadek et al. (2008 ▶). For the anticancer activity of naphthalimides, see: Braña & Ramos (2001 ▶); Braña et al. (2001 ▶); Suárez & Sánchez (1992 ▶); Ingrassia et al. (2009 ▶); Wu et al. (2009 ▶); Norton et al. (2008 ▶). For the therapeutic properties of cyclic imides, see: Cechinel Filho et al. (2003 ▶); Walter et al. (2002 ▶). For background to this study, see: Silva et al. (2006 ▶); Oliveira & Nunes (2006 ▶).

Experimental

Crystal data

C₂₆H₁₈N₄O₆S·C₂H₆OS
M _r = 592.63
Triclinic,
a = 9.152 (1) Å
b = 11.971 (1) Å
c = 13.910 (1) Å
α = 107.268 (7)°
β = 101.789 (7)°
γ = 96.319 (8)°
V = 1400.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 293 K
0.50 × 0.16 × 0.13 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
5055 measured reflections
4737 independent reflections
3075 reflections with I > 2σ(I)
R _int = 0.017
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.163
S = 1.04
4737 reflections
371 parameters
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: HELENA (Spek, 1996 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811004697/ff2001sup1.cif

e-67-0o627-sup1.cif^{(24.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811004697/ff2001Isup2.hkl

e-67-0o627-Isup2.hkl^{(227.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

Cg is the centroid of the p-nitrophenyl (C22–C27) ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O1S	0.80	1.99	2.764 (4)	163
C8—H8⋯Cgⁱ	0.93	2.90	3.799 (6)	162

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank CAPES and CNPq for financial support.

supplementary crystallographic information

Comment

Sulfonyl-hydrazones are known for their therapeutic properties, such as, antimicrobial (Rollas et al. 2002, Frlan et al. 2008), analgesic (Lima et al. 1999, Sondhi et al. 2006), etc. Sulfonyl-hydrazones was selective inhibitor of p110α, a phosphoinositide-3-kinase that is over-expressed in 30% of tumors (Kendall et al. 2007). In innovative study, the sulfonyl-hydrazones were reported by enhance myocardial repair by stem cells by activating cardiac differentiation in human mobilized peripheral blood mononuclear cells (M-PBMCs) (Sadek et al. 2008).

Cyclic imides have also many therapeutic properties including antibacterial, antitumor, diuretic and antiviral (Cechinel Filho et al. 2003). In a previous publication, we reported the synthesis of imidobenzenesulfonyl compounds that showed promising analgesic profiles in the acetic acid- induced mice writhing test. The mechanism of action occurred possibly due to additional non-covalent interactions with the COX active site (Walter et al. 2002). The naphthalimides, in special, are known of their high DNA-binding ability and consequently many of them have anticancer property (Braña & Ramos, 2001); Braña et al. 2001). Mitonafide and Amonafide are classical examples of naphthalimides derivatives with antitumoral activity (Suárez et al. 1992). Recently, many similar compounds have been showed activity against different cancer cell lines (Ingrassia et al. 2009, Wu et al. 2009, Norton et al. 2008).

The title compound (I) (Scheme 1) was synthesized as a part of our work to investigate the antitumoral activity of the sulfonyl-hydrazones cyclic imides derivatives (Oliveira et al. 2006, Silva et al. 2006).

The molecular structure of the title compound (Fig. 1) shows E conformation on the hydrazone double bond, which is evidenced by the torsion angle S1–N2–N3–C21 of 165.8 (2)°. The presence of a methylene group among benzo[de]isoquinoline and benzenesulfonyl moieties allows p-nitrophenyl ring and benzo[de]isoquinoline system to be parallel with respect to each other, so that the molecule adopts an U-shaped spatial conformation. The dihedral angle between mean planes of these planar groups is 4.4 (1)°. This special arrangement enables the neighboring molecule be intercalated by a center of symmetry, forming pairs of molecules in a centrosymmetric structure (Fig. 2). Slipped π–π interaction between p-nitrophenyl and benzo[de]isoquinoline, with centroid–C12 distance of 3.589 Å, and point-to-face C–H···π interaction between benzenesulfonyl and benzo[de]isoquinoline aromatic systems, with centroid-H8 distance of 2.903 Å, are observed. In addition, crystal packing also shows an intermolecular N2–H···O1S interaction involving amine group and DMSO solvate.

Experimental

4-nitrobenzaldehyde (79 mg, 0.52 mmol) was added in a mixture of 4-[(1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)methyl] benzenesulfonohydrazide (200 mg, 0.52 mmol) in ethanol (10 ml), with a drop of hydrochloric acid as catalyst, as described for similar compounds (Silva et al. 2006, Oliveira et al. 2006). The reaction was carried out by stirring at room temperature for one hour. The solid was filtered off with suction. The crystal used for data collection was obtained by dissolving 30 mg of (I) in 10 ml of dimethylsulfoxide and by slow evaporation of the solvent.