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

Cathryn A Slabber; Matthew P Akerman; Ross S Robinson

doi:10.1107/S1600536811014693

. 2011 May 7;67(Pt 6):o1338. doi: 10.1107/S1600536811014693

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

Cathryn A Slabber ^a, Matthew P Akerman ^a, Ross S Robinson ^a,^*

PMCID: PMC3120534 PMID: 21754734

Abstract

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].

Related literature

For the synthesis of the title compound, see: Slabber (2011 ▶). For the structures of related compounds and luminescence studies, see: Weber et al. (2009 ▶).

Experimental

Crystal data

C₁₇H₁₅BN₂S
M _r = 290.18
Monoclinic,
a = 13.7594 (6) Å
b = 9.0545 (3) Å
c = 12.7830 (5) Å
β = 113.411 (5)°
V = 1461.46 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 296 K
0.40 × 0.40 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur 2 CCD diffractometer
Absorption correction: multi-scan CrysAlis RED; Oxford Diffraction, 2008 ▶) T _min = 0.919, T _max = 0.939
14782 measured reflections
4709 independent reflections
2774 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.149
S = 0.98
4709 reflections
199 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON, SHELXL97 and WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811014693/lw2059sup1.cif

e-67-o1338-sup1.cif^{(18.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811014693/lw2059Isup2.hkl

e-67-o1338-Isup2.hkl^{(226KB, hkl)}

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

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

Cg2 is the centroid of the C5–C9 ring and Cg3 is the centroid of the C11–C16 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Cg3ⁱ	0.93	2.75	3.5178 (18)	141
C12—H12⋯Cg2ⁱⁱ	0.93	2.82	3.6122 (17)	144

Open in a new tab

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

Acknowledgments

The authors thank Professor O. Q. Munro and Mr C. R. Wilson (University of KwaZulu-Natal) for the data collection and structure refinement.

supplementary crystallographic information

Comment

C₁₇H₁₅BN₂S, is one compound 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 the phenyl ring systems is 19.86 (6)°. The atoms N1, B1 and N2 lie at 0.053 (2) Å, 0.084 (2) Å and 0.017 (2) Å respectively above the mean plane 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.

There is a π–π interaction between the centrosymmetrically related phenyl rings, containing C8, at (x, y, z) and (1 - x, -y, -z). The centroid-to-centroid distance is 3.5922 (8) Å, with a perpendicular spacing between the planes of 3.3883 (6) Å and a slippage of 1.193 Å.

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 CH₂Cl₂ yielded yellow crystalline material in a yield of 65%. Crystals suitable for X-ray diffraction analysis were grown from CH₂Cl₂ at room temperature.