10-(6-Hy­droxy­hexa-2,4-diyn-1-yl)-10H-phenothia­zine 5-oxide

Hideyuki Tabata; Tsunehisa Okuno

doi:10.1107/S1600536812027511

. 2012 Jun 27;68(Pt 7):o2214. doi: 10.1107/S1600536812027511

10-(6-Hydroxyhexa-2,4-diyn-1-yl)-10H-phenothiazine 5-oxide

Hideyuki Tabata ^a, Tsunehisa Okuno ^a,^*

PMCID: PMC3394009 PMID: 22798874

Abstract

The title compound, C₁₈H₁₃NO₂S, has two independent molecules (A and B) with similar conformations in the asymmetric unit. Both phenothiazine moieties have a butterfly structure [dihedral angles between benzene rings = 155.17 (7) and 161.71 (7)°, respectively], and the central six-membered rings have a boat form. In the crystal, the A and B molecules stack alternately along the b axis. The A and B molecules are linked by O—H⋯O=S hydrogen bonds, forming zigzag chains along [10-1].

Related literature

For related structures of phenothiazine 5-oxide compounds, see: Chu et al. (1985 ▶); Dahl et al. (1982 ▶); Hough et al. (1985a ▶,b ▶, 1982 ▶); Jin et al. (2010 ▶); Jovanovic et al. (1986 ▶); Okuno et al. (2006 ▶); Wang et al. (2009 ▶); Xu et al. (2009 ▶). For the related preparation of 10-(6-hydroxyhexa-2,4-diyn-1-yl)-10H-phenothiazine, see: Zaugg et al. (1958 ▶) and for the preparation of the title compound, see: Gilman & Ranck (1958 ▶).

Experimental

Crystal data

C₁₈H₁₃NO₂S
M _r = 307.37
Monoclinic,
a = 16.797 (5) Å
b = 10.197 (3) Å
c = 17.664 (5) Å
β = 94.934 (5)°
V = 3014.3 (15) Å³
Z = 8
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 93 K
0.15 × 0.15 × 0.05 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: numerical (NUMABS; Rigaku, 1999 ▶) T _min = 0.969, T _max = 0.989
24445 measured reflections
6932 independent reflections
5523 reflections with F ² > 2σ(F ²)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.135
S = 1.08
6931 reflections
404 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.88 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: CrystalStructure (Rigaku, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812027511/ff2072sup1.cif

e-68-o2214-sup1.cif^{(25.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027511/ff2072Isup2.hkl

e-68-o2214-Isup2.hkl^{(339.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812027511/ff2072Isup3.cml

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H13⋯O3ⁱ	0.82 (3)	1.85 (3)	2.663 (3)	172 (3)
O4—H26⋯O1ⁱⁱ	0.85 (2)	1.81 (2)	2.659 (3)	175 (3)

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

Acknowledgments

This work was supported by Research for Promoting Technological Seeds of the Japan Science and Technology Agency (JST).

supplementary crystallographic information

Comment

Aromatic compounds that contain S-atom in a substituent and/or within an aromatic ring have attracted interest from the viewpoint of electronic property of the compounds. Oxidation of S-atom to form S=O bond enables to control its electronic condition without remarkable structural changes. S=O bonds have also been paid attention due to their ability to control the molecular arrangements.

In the title compound, there are two independent molecules (A and B) in the unit cell (Figure 1). The molecular structures of A and B are similar. The phenothiazine moieties have a butterfly structure, where the dihedral angles between two benzene rings (the C1—C6 plane: r.m.s. deviation = 0.0114 Å and the C7—C12 plane: r.m.s. deviation = 0.0020 Å in A, the C19—C24 plane: r.m.s. deviation = 0.0033 Å and the C25—C30 plane: r.m.s. deviation = 0.0052 Å in B) are 155.17 (7)° and 161.71 (7)°, respectively. The central six-membered rings (the N1/C1/C6/S1/C7/C12 and the N2/C19/C24/S2/C25/C30 rings) have a boat form. The S1—O1 and S2—O3 bonds showed longer bond lengths compared with the reported values (1.434 (13) Å - 1.511 (3) Å) of phenothiazine 5-oxide compounds. (Chu et al., 1985; Dahl et al., 1982; Hough et al., 1982; Hough et al., 1985a; Hough et al., 1985b; Jin et al., 2010; Jovanovic et al., 1986; Okuno et al., 2006; Wang et al., 2009; Xu et al., 2009). The elongation might be caused by the intermolecular hydrogen bonds.

The A and B stack alternately along the b axis. There are not any remarkable contacts within the stacks. The A and B molecules are connected by O—H···O=S hydrogen bonds, forming zig-zag chains along the [101] direction, where the distances of O2···O3ⁱ and O4···O1ⁱⁱ [Symmetry codes: (i) -x, y - 1/2, -z + 3/2; (ii) -x + 1, y + 1/2, -z + 1/2] are 2.663 (3) Å and 2.659 (3) Å, respectively (Figure 2). In this compound, S=O bonds play an important role to link the stacks by the intermolecular hydrogen bonds.

Experimental

10-(6-Hydroxyhexa-2,4-diyn-1-yl)-10H-phenothiazine

N¹,N¹,N⁴,N⁴-Tetramethylethylenediamine (TMEDA; 30 µl, 0.20 mmol) was added to a suspension of copper(I) chloride (57 mg, 0.58 mmol) in degassed acetone (4 ml), and the suspension was stirred for 30 min. The supernatant solution containing the CuCl-TMEDA catalyst was transferred to a solution of 10-(prop-2-yn-1-yl)-10H-phenothiazine (0.67 g, 2.82 mmol) (Zaugg et al., 1958) and 2-propyn-1-ol (1.6 ml, 28 mmol) in acetone (3 ml). The solution was stirred for 6 days under an oxygen atmosphere. After the concentration of the solution, the residue was extracted with dichloromethane (20 ml). The solution was washed with 0.5 M aqueous hydrogen chloride (7 ml) and water (20 ml × 3) successively. The water layer was extracted twice with dichloromethane (200 ml). After the concentration of the combined solution, the residue was purified by a recrystallization from a n-hexane to give a 10-(6-hydroxyhexa-2,4-diyn-1-yl)-10H-phenothiazine as a white powder (0.60 g, yield 73%).

10-(6-Hydroxyhexa-2,4-diyn-1-yl)-10H-phenothiazine 5-oxide (Gilman & Ranck, 1958)

To a solution of 10-(6-hydroxyhexa-2,4-diyn-1-yl)-10H-phenothiazine (0.04 g, 0.14 mmol) in ethanol (30 ml), hydrogen peroxide (0.2 ml, 3.9 mmol × 2) was added successively. Then, the solution was refluxed for 5 h. After the solvent was evaporated, the residue was extracted with dichloromethane (20 ml × 3) and washed with water (20 ml). After the organic layer was concentrated, the residue was purified by a column chromatography with dichloromethane/ethanol (50:1 v/v) as an eluent to give 10-(6-hydroxyhexa-2,4-diyn-1-yl)-10H-phenothiazine 5-oxide (0.03 g, yield 71%). The single crystals with sufficient quality for X-ray analysis were obtained by concentration of a chloroform solution.