7-Bromo-2-(4-fluoro­phen­yl)-1-(methyl­sulfin­yl)naphtho[2,1-b]furan

Hong Dae Choi; Pil Ja Seo; Byeng Wha Son; Uk Lee

doi:10.1107/S1600536810011645

. 2010 Apr 2;66(Pt 5):o1012. doi: 10.1107/S1600536810011645

7-Bromo-2-(4-fluorophenyl)-1-(methylsulfinyl)naphtho[2,1-b]furan

Hong Dae Choi ^a, Pil Ja Seo ^a, Byeng Wha Son ^b, Uk Lee ^b,^*

PMCID: PMC2979164 PMID: 21579076

Abstract

In the title compound, C₁₉H₁₂BrFO₂S, the O atom and the methyl group of the methylsulfinyl substituent lie on opposite sides of the plane through the naphthofuran fragment. The 4-fluorophenyl ring is rotated out of the naphthofuran plane, making a dihedral angle of 41.65 (7)°. In the crystal, molecules are linked by weak intermolecular C—H⋯O and C—H⋯π interactions, and a short Br⋯F contact [3.046 (2) Å] occurs. The O atom of the sulfinyl group is disordered over two positions, with refined site-occupancy factors of 0.912 (4) and 0.088 (4).

Related literature

For the crystal structures of similar 7-bromo-2-phenylnaphtho[2,1-b]furan derivatives, see: Choi et al. (2006 ▶, 2009 ▶). For the biological activity of naphthofuran compounds, see: Einhorn et al. (1984 ▶); Hranjec et al. (2003 ▶); Mahadevan & Vaidya (2003 ▶).

Experimental

Crystal data

C₁₉H₁₂BrFO₂S
M _r = 403.26
Monoclinic,
a = 6.0155 (2) Å
b = 22.7143 (6) Å
c = 11.4364 (3) Å
β = 91.716 (1)°
V = 1561.94 (8) Å³
Z = 4
Mo Kα radiation
μ = 2.79 mm⁻¹
T = 173 K
0.31 × 0.28 × 0.16 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.515, T _max = 0.746
14194 measured reflections
3547 independent reflections
3086 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.078
S = 1.09
3547 reflections
228 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.66 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 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810011645/zl2274sup1.cif

e-66-o1012-sup1.cif^{(20KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810011645/zl2274Isup2.hkl

e-66-o1012-Isup2.hkl^{(174KB, hkl)}

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

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

Cg is the centroid of the C2/C3/C8/C9/C10/C11 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯O2Aⁱ	0.93	2.53	3.235 (3)	133
C18—H18⋯Cgⁱⁱ	0.93	2.65	3.347 (3)	132

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

supplementary crystallographic information

Comment

Many compounds containing naphthofuran moieties show potent biological activities such as antibacterial (Einhorn et al., 1984), antitumor (Hranjec et al., 2003) and anthelmintic (Mahadevan & Vaidya, 2003) properties. As a part of our continuing studies of the effect of side chain substituents on the solid state structures of 7-bromo-2-phenylnaphtho[2,1-b]furan analogues (Choi et al., 2006, 2009), we report the crystal structure of the title compound (Fig. 1).

The naphthofuran unit is essentially planar, with a mean deviation of 0.040 (2) Å from the least-squares plane defined by the thirteen constituent atoms. The oxygen of the sulfinyl group is disordered over two positions with site-occupancy factors of 0.912 (4) (for O atom labeled A) and 0.088 (4) (for O atom labeled B). The dihedral angle formed by the naphthofuran plane and the 4-fluorophenyl ring is 41.65 (7)°. The crystal packing (Fig. 2) is stabilized by intermolecular C–H···O hydrogen bonds between the 4-fluorophenyl H atom H14 and the oxygen O2Aⁱ of the S═O unit. The molecular packing (Fig. 2) is further stabilized by intermolecular C–H···π interactions between the 4-fluorophenyl H atom H18 and the centroid Cgⁱⁱ of the central benzene ring of an adjacent naphthofuran system (see Table 1 for numerical values and symmetry operators; Cg is the centroid of the atoms C2/C3/C8/C9/C10/C11 of the benzene ring). Furthermore, a short Br···F^iv contact (Fig. 2) [3.046 (2) Å] provides additional stabilization.

Experimental

77% 3-Chloroperoxybenzoic acid (202 mg, 0.9 mmol) was added in small portions to a stirred solution of 7-bromo-2-(4-fluorophenyl)-1-(methylsulfanyl)naphtho[2,1-b]furan (310 mg, 0.8 mmol) in dichloromethane (30 mL) at 273 K. After being stirred at room temperature for 5h, the mixture was washed with saturated sodium bicarbonate solution and the organic layer was separated, dried over magnesium sulfate, filtered and concentrated at reduced pressure. The residue was purified by column chromatography (hexane-ethyl acetate, 1:1 v/v) to afford the title compound as a colorless solid [yield 76%, m.p. 501-502 K; R_f = 0.66 (hexane-ethyl acetate, 1:1 v/v)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in chloroform at room temperature.