7-Bromo-1-(4-chloro­phenyl­sulfan­yl)-2-phenyl­naphtho[2,1-b]furan

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

doi:10.1107/S1600536809052945

. 2009 Dec 16;66(Pt 1):o173. doi: 10.1107/S1600536809052945

7-Bromo-1-(4-chlorophenylsulfanyl)-2-phenylnaphtho[2,1-b]furan

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

PMCID: PMC2980269 PMID: 21580059

Abstract

In the title compound, C₂₄H₁₄BrClOS, the S-bound 4-chlorophenyl ring is nearly perpendicular to the plane of the naphthofuran fragment [dihedral angle = 83.34 (3)°] and the phenyl ring in the 2-position is rotated out of the naphthofuran plane by a dihedral angle of 15.23 (5)°. The crystal structure is stabilized by aromatic π–π interactions between the furan and the central benzene rings of the neighbouring naphthofuran fragments, and between the outer benzene rings of the neighbouring naphthofuran fragments; the centroid–centroid distances within the stack are 3.879 (2) and 3.857 (2) Å. In addition, intermolecular C—Cl⋯π interactions [3.505 (2) Å] between the Cl atom and the 2-phenyl ring are present.

Related literature

For the crystal structures of similar 7-bromo-2-phenylnaphtho[2,1-b]furan derivatives, see: Choi et al. (2009a ▶,b ▶). For the biological activity of naphthofuran compounds, see: Hagiwara et al. (1999 ▶); Hranjec et al. (2003 ▶); Mahadevan & Vaidya (2003 ▶).

Experimental

Crystal data

C₂₄H₁₄BrClOS
M _r = 465.77
Triclinic,
a = 8.2479 (3) Å
b = 8.3136 (4) Å
c = 13.9805 (6) Å
α = 93.530 (2)°
β = 99.317 (2)°
γ = 90.342 (2)°
V = 944.07 (7) Å³
Z = 2
Mo Kα radiation
μ = 2.44 mm⁻¹
T = 173 K
0.40 × 0.20 × 0.05 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.560, T _max = 0.887
16830 measured reflections
4364 independent reflections
3912 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.026
wR(F ²) = 0.068
S = 1.05
4364 reflections
253 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.33 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/S1600536809052945/bg2314sup1.cif

e-66-0o173-sup1.cif^{(20.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809052945/bg2314Isup2.hkl

e-66-0o173-Isup2.hkl^{(213.8KB, hkl)}

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

supplementary crystallographic information

Comment

Molecules bearing naphthofuran skeleton have attracted considerable interest in view of their biological activity (Hagiwara et al., 1999; Hranjec et al., 2003; Mahadevan & Vaidya, 2003). 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., 2009a, b), we report the crystal structure of the title compound (Fig. 1).

The naphthofuran unit is essentially planar, with a mean deviation of 0.009 (1) Å from the least-squares plane defined by the thirteen constituent atoms. In the crystal structure, the dihedral angle formed by the plane of the naphthofuran fragment and the 2-phenyl ring (C13–C18) is 15.23 (5)°, and the S-bound 4-chlorophenyl ring makes a diheral angle of 83.34 (3)° with the plane of the naphthofuran fragment. The crystal packing (Fig. 2) is stabilized by two different aromatic π–π interactions within each stack molecules; the first between the furan ring (Cg1) and the central benzene ring (Cg2ⁱ, (i): - x + 1, - y + 1, - z + 1) of the neighbouring naphthofuran units [distance; 3.879 (2) Å], and the second between the outer benzene ring (Cg3) and the outer benzene ring (Cg3ⁱⁱ, (ii): - x + 1, - y, - z + 1) of the neighbouring naphthofuran units [distance; 3.857 (2)Å] (Cg1, Cg2 and Cg3 are the centroides of the C1/C2/C11/O/C12 furan ring, the C2/C3/C8/C9/C10/C11 benzene ring and the C3–C8 benzene ring, respectively). The molecular packing (Fig. 2) is further stabilized by intermolecular C—Cl···π interactions between the chlorine and the phenyl ring (Cg4), with a C22—Cl···Cg4ⁱⁱⁱ [3.505 (2) Å] (Cg4 is the centroid of the C13–C18 benzene ring, (iii): - x + 1, - y, - z).

Experimental

Zinc chloride (273 mg, 2.0 mmol) was added to a stirred solution of 6-bromonaphthol (446 mg, 2.0 mmol) and 2-chloro-2-(4-chlorophenylsulfanyl)acetophenone (594 mg, 2.0 mmol) in dichloromethane (40 ml) at room temperature, and stirring was continued at the same temperature for 40 min. The reaction was quenched by the addition of water and the organic layer separated, dried over magnesium sulfate, filtered and concentrated in vacuum. The residue was purified by column chromatography (carbon tetrachloride) to afford the title compound as a colorless solid [yield 74%, m.p. 481–482 K; R_f = 0.8 (carbon tetrachloride)]. Single crystals suitable for X-ray diffraction were prepared by evaporation of a solution of the title compound in tetrahydrofuran at room temperature.