Crystal structure of 6-(p-tolyl)benzo[b]naphtho[2,3-d]thiophene and of an orthorhombic polymorph of 7-phenylanthra[2,3-b]benzo[d]thiophene

The title compounds, 6-(p-tolyl)benzo[b]naphtho[2,3-d]thiophene and 7-phenylanthra[2,3-b]benzo[d]thiophene, are benzothiophene derivatives in which the benzothiophene moiety is fused with a naphthalene ring system in the former and with an anthracene ring system in the latter. In the former, the 4-methylbenzene ring substituent makes a dihedral angle of 71.40 (9)° with the mean plane of the naphthalene ring system, while the phenyl ring substituent in the latter makes a dihedral angle of 67.08 (12)° with the mean plane of the anthracene ring system.


Chemical context
The thiophene nucleus has been shown to be an important heterocyclic unit in compounds possessing promising pharmacological characteristics, such as anti-HIV PR inhibitors (Bonini et al., 2005) and anti-breast cancer (Brault et al., 2005) activities. Benzothiophenes are important biologically active molecules. One of the most important drugs based on the benzothiophene system is Raloxifine, used for the prevention and treatment of osteoporosis in postmenopausal women (Jordan, 2003). Benzothiophenes are also present in luminescent components used in organic materials (Russell & Press, 1996).

Structural commentary
The molecular structures of the title compounds, (I) and (II), are illustrated in Figs. 1 and 2, respectively. In both compounds, the benzothiophene ring systems are almost planar with the dihedral angles between the benzene and thiophene rings being 1.85 (11) in (I) and 0.56 (18) in (II).
In the triclinic polymorph of compound (II) , the major component of the disordered phenyl ring substituent makes a dihedral angle of 79.39 (12) with the anthracene ring system.

Supramolecular features
In the crystals of both compounds, molecules are linked by C-HÁ Á Á interactions (see Tables 1 and 2) The molecular structure of compound (II), showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Figure 1
The molecular structure of compound (I), showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Figure 3
The crystal packing of compound (I). The C-HÁ Á Á interactions are shown as dashed lines (see Table 1 for details). H atoms not involved in these interactions have been omitted for clarity.

Figure 5
The crystal packing of compound (I), viewed along the c axis, showing the C-HÁ Á Á interactions (represented as turquoise lines) leading to the formation of slabs parallel to (001).

Figure 4
The crystal packing of compound (II), viewed along the b axis. The C-HÁ Á Á interactions are shown as dashed lines (see Table 2 for details) and the centroids as brown balls. H atoms not involved in these interactions have been omitted for clarity. (I),

Refinement
Crystal data, data collection and structure refinement details for compounds (I) and (II) are summarized in Table 3. The C-bound H atoms were included in calculated positions and treated as riding atoms, with C-H = 0.93-0.96 Å and with U iso (H) = 1.5U eq (methyl C) and 1.2U eq (C) for other H atoms.

(I) 6-(p-Tolyl)benzo[b]naphtho[2,3-d]thiophene
Crystal data where P = (F o 2 + 2F c 2 )/3 (Δ/σ) max = 0.002 Δρ max = 0.21 e Å −3 Δρ min = −0.21 e Å −3 Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > 2sigma(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.  (18) C4-S1-C3 91.52 (9) C14-C13-C12 121.6 (2) 177.9 (2) S1-C4-C9-C10 2.0 (2) C17-C18-C19-C20 0.3 (4) C2-C3-C10-C11 0.9 (3) C18-C19-C20-C21 0.4 (4) S1-C3-C10-C11 −179.04 (15) C18-C19-C20-C23 −179.5 (2) C2-C3-C10-C9 179.87 (17) C19-C20-C21-C22 −0.6 (4) S1-C3-C10-C9 0.0 (2) C23-C20-C21-  where P = (F o 2 + 2F c 2 )/3 (Δ/σ) max < 0.001 Δρ max = 1.06 e Å −3 Δρ min = −0.40 e Å −3 Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > 2sigma(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.