2-[4-(Methylsulfanyl)phenyl]naphtho[1,8-de][1,3,2]diazaborinane

The title compound, C17H15BN2S, is one member in a series of diazaborinanes featuring substitution at the 1-, 2- and 3-positions in the nitrogen–boron heterocycle. The dihedral angle between the mean planes of the naphthalene and phenyl ring systems is 19.86 (6)°. In the crystal structure, two C—H⋯π interactions link the molecules into sheets which lie parallel to the bc plane. There is a π–π interaction between each pair of centrosymmetrically related sheets [centroid–centroid distance = 3.5922 (8) Å].

The title compound, C 17 H 15 BN 2 S, is one member in a series of diazaborinanes featuring substitution at the 1-, 2-and 3-positions in the nitrogen-boron heterocycle. The dihedral angle between the mean planes of the naphthalene and phenyl ring systems is 19.86 (6) . In the crystal structure, two C-HÁ Á Á interactions link the molecules into sheets which lie parallel to the bc plane. There is ainteraction between each pair of centrosymmetrically related sheets [centroidcentroid distance = 3.5922 (8) Å ].   Table 1 Hydrogen-bond geometry (Å , ).
of the naphthalene ring.
The H atoms attached to the N atoms are unavailable for hydrogen-bonding due to their positions in the molecule.
The supramolecular structure is determined by the C2-H2···Cg3(x, 0.5 -y, -0.5 + z) and the C12-H12···Cg2(x, -0.5 -y, 0.5 + z), where Cg3 is the centroid of the phenyl ring containing C11 and Cg2 is the centroid of the phenyl ring containing C8. These link the molecules into sheets which lie in the bc plane.

Experimental
To a solution of 1,8-diaminonaphthalene in toluene (4.11 mmol in 50 ml, 0.82 M) (Slabber, 2011) was added the 4-(methylthio)phenylboronic acid (4.11 mmol) in one portion. The round-bottomed flask was equipped with a Dean and Stark trap, and the solution was stirred and heated at 110°C for 3 h. The solvent was removed in vacuo and column chromatography of the crude solid on silica eluting with CH 2 Cl 2 yielded yellow crystalline material in a yield of 65%. Crystals suitable for X-ray diffraction analysis were grown from CH 2 Cl 2 at room temperature.

Refinement
H atoms were treated as riding atoms with C-H(aromatic), 0.93 Å, with U iso = 1.2U eq (C) and C-H3 (methyl), 0.96Å, with U iso = 1.5U eq (C). H atoms attached to N atoms were located on a difference map, and allowed to refine.

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 supplementary materials sup-3 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 > 2σ(F 2 ) is used only for calculating Rfactors(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.