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

Tabata, H.; Okuno, T.

doi:10.1107/S1600536812027511

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2214

https://doi.org/10.1107/S1600536812027511

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

Hideyuki Tabata ^a and Tsunehisa Okuno ^a ^*

^aDepartment of Material Science and Chemistry, Wakayama University, Sakaedani, Wakayama 640-8510, Japan
^*Correspondence e-mail: okuno@center.wakayama-u.ac.jp

(Received 11 June 2012; accepted 18 June 2012; online 27 June 2012)

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, P 2₁ /c
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 F² > 2σ(F²)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 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

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)
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812027511/ff2072sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812027511/ff2072Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812027511/ff2072Isup3.cml

checkCIF report

Comment top

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.

Related literature top

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 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 top

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.

Structure description top

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); 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).

Figures top

	Fig. 1. The asymmetric unit of the title compound with atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres.
	Fig. 2. A view of the two-dimensional array of the title compound on the (101) plane. Hydrogen bonds are shown as dashed lines, and hydrogen atoms are omitted for clarity. [Symmetry codes: (i) -x, y - 1/2, -z + 3/2; (ii) -x + 1, y + 1/2, -z + 1/2; (iii) -x, y + 1/2, -z + 3/2; (iv) -x + 1, y - 1/2, -z + 1/2; (v) x, y - 1, z].

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

Crystal data top

C₁₈H₁₃NO₂S	F(000) = 1280.00
M_r = 307.37	D_x = 1.355 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 9306 reflections
a = 16.797 (5) Å	θ = 2.3–31.2°
b = 10.197 (3) Å	µ = 0.22 mm⁻¹
c = 17.664 (5) Å	T = 93 K
β = 94.934 (5)°	Prism, colourless
V = 3014.3 (15) Å³	0.15 × 0.15 × 0.05 mm
Z = 8

Data collection top

Rigaku Saturn724+ diffractometer	5523 reflections with F² > 2σ(F²)
Detector resolution: 7.111 pixels mm^-1	R_int = 0.033
ω scans	θ_max = 27.5°
Absorption correction: numerical (NUMABS; Rigaku, 1999)	h = −21→21
T_min = 0.969, T_max = 0.989	k = −13→11
24445 measured reflections	l = −22→22
6932 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0692P)² + 0.9115P] where P = (F_o² + 2F_c²)/3
6931 reflections	(Δ/σ)_max = 0.001
404 parameters	Δρ_max = 0.88 e Å⁻³
1 restraint	Δρ_min = −0.47 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₈H₁₃NO₂S	V = 3014.3 (15) Å³
M_r = 307.37	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.797 (5) Å	µ = 0.22 mm⁻¹
b = 10.197 (3) Å	T = 93 K
c = 17.664 (5) Å	0.15 × 0.15 × 0.05 mm
β = 94.934 (5)°

Data collection top

Rigaku Saturn724+ diffractometer	6932 independent reflections
Absorption correction: numerical (NUMABS; Rigaku, 1999)	5523 reflections with F² > 2σ(F²)
T_min = 0.969, T_max = 0.989	R_int = 0.033
24445 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	1 restraint
wR(F²) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.88 e Å⁻³
6931 reflections	Δρ_min = −0.47 e Å⁻³
404 parameters

Special details top

Refinement. Refinement was performed using all reflections except for 1 with very negative F². The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.30626 (3)	0.37416 (5)	0.39495 (3)	0.02511 (13)
S2	0.16339 (3)	0.80322 (5)	0.61113 (3)	0.02991 (14)
O1	0.36361 (8)	0.25896 (13)	0.40014 (8)	0.0299 (3)
O2	−0.10191 (8)	0.61158 (15)	0.80031 (8)	0.0280 (3)
O3	0.09579 (9)	0.90034 (15)	0.61077 (10)	0.0420 (4)
O4	0.61087 (8)	0.67228 (15)	0.23764 (8)	0.0326 (4)
N1	0.25753 (9)	0.34698 (15)	0.55932 (8)	0.0206 (4)
N2	0.23463 (9)	0.90242 (15)	0.46339 (9)	0.0249 (4)
C1	0.20387 (11)	0.29706 (17)	0.50186 (10)	0.0212 (4)
C2	0.13522 (11)	0.22802 (18)	0.51913 (11)	0.0255 (4)
C3	0.08004 (12)	0.18508 (19)	0.46171 (11)	0.0292 (5)
C4	0.09045 (12)	0.20915 (19)	0.38558 (11)	0.0298 (5)
C5	0.15870 (12)	0.27348 (18)	0.36725 (11)	0.0278 (5)
C6	0.21564 (11)	0.31566 (17)	0.42466 (10)	0.0233 (4)
C7	0.33286 (12)	0.47585 (18)	0.47324 (11)	0.0251 (4)
C8	0.38433 (13)	0.5795 (2)	0.45994 (12)	0.0341 (5)
C9	0.41471 (14)	0.6578 (3)	0.51915 (13)	0.0388 (6)
C10	0.39262 (13)	0.6322 (2)	0.59173 (12)	0.0346 (5)
C11	0.34146 (12)	0.53097 (19)	0.60589 (11)	0.0274 (4)
C12	0.31011 (11)	0.44917 (17)	0.54639 (10)	0.0221 (4)
C13	0.24625 (11)	0.31145 (18)	0.63824 (10)	0.0224 (4)
C14	0.18691 (11)	0.39347 (18)	0.67257 (10)	0.0234 (4)
C15	0.13874 (11)	0.46074 (18)	0.70120 (10)	0.0234 (4)
C16	0.08236 (11)	0.53360 (18)	0.73504 (10)	0.0246 (4)
C17	0.03417 (11)	0.59378 (18)	0.76754 (11)	0.0251 (4)
C18	−0.02351 (11)	0.6651 (2)	0.81011 (12)	0.0286 (5)
C19	0.18737 (11)	0.78941 (18)	0.45680 (11)	0.0244 (4)
C20	0.16976 (12)	0.72862 (18)	0.38549 (11)	0.0273 (5)
C21	0.12277 (12)	0.61690 (19)	0.37921 (12)	0.0286 (5)
C22	0.09196 (12)	0.56089 (19)	0.44271 (12)	0.0294 (5)
C23	0.10966 (12)	0.61816 (19)	0.51256 (12)	0.0286 (5)
C24	0.15653 (11)	0.73151 (18)	0.52011 (11)	0.0255 (4)
C25	0.25119 (11)	0.89494 (19)	0.60253 (11)	0.0266 (4)
C26	0.29188 (12)	0.9335 (2)	0.67147 (12)	0.0298 (5)
C27	0.35514 (12)	1.0200 (2)	0.67242 (12)	0.0328 (5)
C28	0.37838 (12)	1.0661 (2)	0.60378 (13)	0.0327 (5)
C29	0.34015 (12)	1.02790 (19)	0.53504 (12)	0.0290 (5)
C30	0.27439 (11)	0.94121 (18)	0.53302 (11)	0.0248 (4)
C31	0.25409 (12)	0.96831 (19)	0.39337 (11)	0.0278 (4)
C32	0.31969 (12)	0.90391 (19)	0.35750 (11)	0.0282 (5)
C33	0.37120 (12)	0.8436 (2)	0.32972 (11)	0.0280 (5)
C34	0.42881 (12)	0.77033 (19)	0.29766 (11)	0.0277 (5)
C35	0.47657 (12)	0.70260 (19)	0.26922 (11)	0.0272 (4)
C36	0.53335 (11)	0.6173 (2)	0.23356 (12)	0.0287 (5)
H1	0.1266	0.2107	0.5706	0.0306*
H2	0.0342	0.1383	0.4745	0.0350*
H3	0.0513	0.1818	0.3468	0.0358*
H4	0.1670	0.2891	0.3155	0.0334*
H5	0.3984	0.5960	0.4099	0.0410*
H6	0.4501	0.7279	0.5105	0.0465*
H7	0.4133	0.6860	0.6327	0.0415*
H8	0.3273	0.5163	0.6561	0.0328*
H9	0.2981	0.3191	0.6691	0.0269*
H10	0.2291	0.2187	0.6398	0.0269*
H11	−0.0049	0.6636	0.8648	0.0343*
H12	−0.0254	0.7578	0.7934	0.0343*
H13	−0.1010 (16)	0.542 (3)	0.8238 (16)	0.050 (8)*
H14	0.1903	0.7646	0.3415	0.0328*
H15	0.1113	0.5776	0.3308	0.0344*
H16	0.0594	0.4847	0.4377	0.0353*
H17	0.0898	0.5802	0.5563	0.0343*
H18	0.2758	0.8998	0.7179	0.0357*
H19	0.3822	1.0475	0.7191	0.0394*
H20	0.4219	1.1257	0.6041	0.0393*
H21	0.3581	1.0600	0.4890	0.0348*
H22	0.2692	1.0603	0.4053	0.0333*
H23	0.2059	0.9697	0.3569	0.0333*
H24	0.5357	0.5310	0.2593	0.0344*
H25	0.5142	0.6029	0.1796	0.0344*
H26	0.6186 (16)	0.695 (3)	0.1926 (11)	0.0489*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0337 (3)	0.0229 (3)	0.0194 (3)	0.00180 (18)	0.00666 (19)	0.00054 (17)
S2	0.0313 (3)	0.0278 (3)	0.0311 (3)	−0.0024 (2)	0.0052 (2)	−0.0050 (2)
O1	0.0342 (8)	0.0273 (8)	0.0292 (7)	0.0066 (6)	0.0081 (6)	−0.0021 (6)
O2	0.0261 (7)	0.0278 (8)	0.0304 (8)	0.0005 (6)	0.0040 (6)	0.0057 (6)
O3	0.0294 (8)	0.0407 (9)	0.0559 (11)	−0.0002 (7)	0.0047 (7)	−0.0241 (8)
O4	0.0266 (8)	0.0436 (9)	0.0273 (8)	−0.0095 (7)	0.0008 (6)	0.0045 (7)
N1	0.0240 (8)	0.0213 (8)	0.0168 (7)	0.0002 (6)	0.0031 (6)	−0.0001 (6)
N2	0.0271 (8)	0.0201 (8)	0.0273 (8)	0.0003 (7)	0.0015 (7)	−0.0018 (7)
C1	0.0260 (9)	0.0176 (9)	0.0198 (9)	0.0040 (7)	0.0010 (7)	−0.0010 (7)
C2	0.0289 (10)	0.0254 (10)	0.0225 (9)	0.0017 (8)	0.0039 (8)	−0.0012 (8)
C3	0.0273 (10)	0.0264 (11)	0.0334 (11)	−0.0005 (8)	0.0002 (9)	−0.0041 (8)
C4	0.0326 (11)	0.0275 (11)	0.0280 (10)	0.0022 (9)	−0.0059 (9)	−0.0067 (8)
C5	0.0382 (11)	0.0230 (10)	0.0216 (9)	0.0084 (8)	−0.0010 (8)	−0.0037 (8)
C6	0.0307 (10)	0.0176 (9)	0.0216 (9)	0.0062 (8)	0.0029 (8)	−0.0004 (7)
C7	0.0315 (10)	0.0196 (10)	0.0246 (9)	0.0011 (8)	0.0052 (8)	0.0013 (8)
C8	0.0474 (13)	0.0270 (11)	0.0294 (11)	−0.0044 (9)	0.0110 (10)	0.0041 (9)
C9	0.0478 (14)	0.0278 (12)	0.0414 (13)	−0.0128 (10)	0.0075 (11)	−0.0005 (10)
C10	0.0398 (12)	0.0298 (12)	0.0336 (11)	−0.0058 (9)	0.0003 (10)	−0.0047 (9)
C11	0.0304 (10)	0.0276 (11)	0.0239 (10)	−0.0011 (8)	0.0018 (8)	−0.0020 (8)
C12	0.0234 (9)	0.0190 (9)	0.0242 (9)	0.0022 (7)	0.0031 (8)	0.0000 (7)
C13	0.0242 (9)	0.0266 (10)	0.0166 (8)	0.0022 (8)	0.0021 (7)	0.0020 (7)
C14	0.0256 (9)	0.0262 (10)	0.0182 (9)	−0.0027 (8)	0.0009 (8)	0.0013 (7)
C15	0.0286 (10)	0.0233 (10)	0.0184 (9)	−0.0027 (8)	0.0030 (8)	0.0003 (7)
C16	0.0277 (10)	0.0245 (10)	0.0217 (9)	−0.0012 (8)	0.0029 (8)	0.0015 (8)
C17	0.0286 (10)	0.0225 (10)	0.0244 (9)	−0.0015 (8)	0.0040 (8)	0.0021 (8)
C18	0.0275 (10)	0.0269 (11)	0.0324 (11)	0.0007 (8)	0.0089 (9)	−0.0027 (9)
C19	0.0223 (9)	0.0191 (9)	0.0313 (10)	0.0035 (7)	−0.0009 (8)	−0.0023 (8)
C20	0.0300 (10)	0.0230 (10)	0.0284 (10)	0.0052 (8)	−0.0010 (8)	−0.0006 (8)
C21	0.0312 (11)	0.0215 (10)	0.0324 (11)	0.0036 (8)	−0.0022 (9)	−0.0062 (8)
C22	0.0273 (10)	0.0185 (10)	0.0420 (12)	0.0001 (8)	0.0002 (9)	−0.0032 (9)
C23	0.0268 (10)	0.0238 (10)	0.0355 (11)	0.0002 (8)	0.0036 (9)	0.0013 (8)
C24	0.0242 (10)	0.0227 (10)	0.0296 (10)	0.0033 (8)	0.0013 (8)	−0.0037 (8)
C25	0.0259 (10)	0.0219 (10)	0.0317 (10)	0.0029 (8)	−0.0001 (8)	−0.0034 (8)
C26	0.0306 (11)	0.0282 (11)	0.0302 (10)	0.0071 (9)	0.0002 (9)	−0.0032 (9)
C27	0.0294 (11)	0.0300 (11)	0.0371 (12)	0.0065 (9)	−0.0087 (9)	−0.0051 (9)
C28	0.0268 (10)	0.0239 (11)	0.0461 (13)	−0.0006 (8)	−0.0048 (9)	−0.0044 (9)
C29	0.0263 (10)	0.0236 (10)	0.0364 (11)	0.0019 (8)	−0.0009 (9)	0.0002 (9)
C30	0.0252 (9)	0.0185 (9)	0.0298 (10)	0.0043 (8)	−0.0027 (8)	−0.0032 (8)
C31	0.0331 (11)	0.0193 (10)	0.0304 (10)	0.0027 (8)	−0.0000 (9)	0.0022 (8)
C32	0.0335 (11)	0.0228 (10)	0.0280 (10)	−0.0026 (8)	0.0012 (9)	0.0030 (8)
C33	0.0324 (11)	0.0256 (10)	0.0257 (10)	−0.0044 (9)	0.0016 (8)	0.0046 (8)
C34	0.0313 (11)	0.0273 (11)	0.0245 (10)	−0.0044 (8)	0.0022 (8)	0.0013 (8)
C35	0.0289 (10)	0.0270 (10)	0.0254 (10)	−0.0055 (8)	0.0009 (8)	0.0038 (8)
C36	0.0250 (10)	0.0285 (11)	0.0328 (11)	−0.0044 (8)	0.0040 (8)	−0.0010 (9)

Geometric parameters (Å, º) top

S1—O1	1.5169 (15)	C25—C26	1.400 (3)
S1—C6	1.757 (2)	C25—C30	1.402 (3)
S1—C7	1.755 (2)	C26—C27	1.380 (3)
S2—O3	1.5063 (17)	C27—C28	1.387 (4)
S2—C24	1.761 (2)	C28—C29	1.380 (3)
S2—C25	1.764 (2)	C29—C30	1.413 (3)
O2—C18	1.422 (3)	C31—C32	1.472 (3)
O4—C36	1.414 (3)	C32—C33	1.200 (3)
N1—C1	1.394 (3)	C33—C34	1.382 (3)
N1—C12	1.397 (3)	C34—C35	1.201 (3)
N1—C13	1.468 (3)	C35—C36	1.472 (3)
N2—C19	1.398 (3)	O2—H13	0.82 (3)
N2—C30	1.405 (3)	O4—H26	0.85 (2)
N2—C31	1.469 (3)	C2—H1	0.950
C1—C2	1.407 (3)	C3—H2	0.950
C1—C6	1.407 (3)	C4—H3	0.950
C2—C3	1.385 (3)	C5—H4	0.950
C3—C4	1.393 (3)	C8—H5	0.950
C4—C5	1.383 (3)	C9—H6	0.950
C5—C6	1.400 (3)	C10—H7	0.950
C7—C8	1.398 (3)	C11—H8	0.950
C7—C12	1.405 (3)	C13—H9	0.990
C8—C9	1.378 (3)	C13—H10	0.990
C9—C10	1.390 (4)	C18—H11	0.990
C10—C11	1.380 (3)	C18—H12	0.990
C11—C12	1.408 (3)	C20—H14	0.950
C13—C14	1.471 (3)	C21—H15	0.950
C14—C15	1.205 (3)	C22—H16	0.950
C15—C16	1.380 (3)	C23—H17	0.950
C16—C17	1.201 (3)	C26—H18	0.950
C17—C18	1.469 (3)	C27—H19	0.950
C19—C20	1.412 (3)	C28—H20	0.950
C19—C24	1.403 (3)	C29—H21	0.950
C20—C21	1.385 (3)	C31—H22	0.990
C21—C22	1.397 (3)	C31—H23	0.990
C22—C23	1.374 (3)	C36—H24	0.990
C23—C24	1.398 (3)	C36—H25	0.990

O1—S1—C6	106.32 (9)	C31—C32—C33	175.7 (2)
O1—S1—C7	107.01 (9)	C32—C33—C34	178.0 (3)
C6—S1—C7	97.68 (10)	C33—C34—C35	177.3 (3)
O3—S2—C24	106.20 (10)	C34—C35—C36	178.5 (2)
O3—S2—C25	106.65 (10)	O4—C36—C35	111.80 (17)
C24—S2—C25	97.53 (10)	C18—O2—H13	107.0 (18)
C1—N1—C12	122.09 (15)	C36—O4—H26	106.0 (17)
C1—N1—C13	118.22 (15)	C1—C2—H1	119.704
C12—N1—C13	118.30 (14)	C3—C2—H1	119.707
C19—N2—C30	121.91 (16)	C2—C3—H2	119.339
C19—N2—C31	118.21 (16)	C4—C3—H2	119.344
C30—N2—C31	119.01 (16)	C3—C4—H3	120.499
N1—C1—C2	121.03 (17)	C5—C4—H3	120.487
N1—C1—C6	121.34 (17)	C4—C5—H4	119.860
C2—C1—C6	117.62 (16)	C6—C5—H4	119.855
C1—C2—C3	120.59 (18)	C7—C8—H5	119.862
C2—C3—C4	121.32 (19)	C9—C8—H5	119.853
C3—C4—C5	119.01 (18)	C8—C9—H6	120.631
C4—C5—C6	120.28 (18)	C10—C9—H6	120.638
S1—C6—C1	122.19 (14)	C9—C10—H7	119.087
S1—C6—C5	116.32 (15)	C11—C10—H7	119.090
C1—C6—C5	121.07 (18)	C10—C11—H8	119.778
S1—C7—C8	115.68 (16)	C12—C11—H8	119.773
S1—C7—C12	122.63 (15)	N1—C13—H9	108.873
C8—C7—C12	121.46 (18)	N1—C13—H10	108.869
C7—C8—C9	120.3 (2)	C14—C13—H9	108.874
C8—C9—C10	118.7 (2)	C14—C13—H10	108.874
C9—C10—C11	121.8 (2)	H9—C13—H10	107.721
C10—C11—C12	120.45 (19)	O2—C18—H11	108.960
N1—C12—C7	121.36 (16)	O2—C18—H12	108.959
N1—C12—C11	121.39 (17)	C17—C18—H11	108.953
C7—C12—C11	117.25 (17)	C17—C18—H12	108.954
N1—C13—C14	113.48 (15)	H11—C18—H12	107.770
C13—C14—C15	179.47 (19)	C19—C20—H14	119.777
C14—C15—C16	177.9 (2)	C21—C20—H14	119.778
C15—C16—C17	177.0 (2)	C20—C21—H15	119.346
C16—C17—C18	177.8 (2)	C22—C21—H15	119.332
O2—C18—C17	113.11 (17)	C21—C22—H16	120.648
N2—C19—C20	120.65 (18)	C23—C22—H16	120.628
N2—C19—C24	121.76 (17)	C22—C23—H17	119.548
C20—C19—C24	117.58 (17)	C24—C23—H17	119.561
C19—C20—C21	120.45 (19)	C25—C26—H18	119.757
C20—C21—C22	121.32 (19)	C27—C26—H18	119.744
C21—C22—C23	118.72 (19)	C26—C27—H19	120.657
C22—C23—C24	120.9 (2)	C28—C27—H19	120.645
S2—C24—C19	123.61 (15)	C27—C28—H20	119.032
S2—C24—C23	114.99 (16)	C29—C28—H20	119.052
C19—C24—C23	121.02 (18)	C28—C29—H21	119.919
S2—C25—C26	115.02 (16)	C30—C29—H21	119.915
S2—C25—C30	123.47 (14)	N2—C31—H22	109.035
C26—C25—C30	121.04 (18)	N2—C31—H23	109.035
C25—C26—C27	120.5 (2)	C32—C31—H22	109.032
C26—C27—C28	118.70 (19)	C32—C31—H23	109.027
C27—C28—C29	121.92 (19)	H22—C31—H23	107.797
C28—C29—C30	120.2 (2)	O4—C36—H24	109.253
N2—C30—C25	121.68 (17)	O4—C36—H25	109.261
N2—C30—C29	120.66 (18)	C35—C36—H24	109.256
C25—C30—C29	117.66 (18)	C35—C36—H25	109.256
N2—C31—C32	112.79 (16)	H24—C36—H25	107.939

O1—S1—C6—C1	77.83 (14)	C2—C1—C6—C5	3.6 (3)
O1—S1—C6—C5	−94.80 (13)	C6—C1—C2—C3	−2.6 (3)
O1—S1—C7—C8	94.67 (14)	C1—C2—C3—C4	−0.3 (3)
O1—S1—C7—C12	−79.86 (16)	C2—C3—C4—C5	2.2 (3)
C6—S1—C7—C8	−155.59 (13)	C3—C4—C5—C6	−1.1 (3)
C6—S1—C7—C12	29.88 (16)	C4—C5—C6—S1	170.93 (15)
C7—S1—C6—C1	−32.48 (15)	C4—C5—C6—C1	−1.8 (3)
C7—S1—C6—C5	154.89 (12)	S1—C7—C8—C9	−174.02 (13)
O3—S2—C24—C19	82.48 (15)	S1—C7—C12—N1	−6.9 (3)
O3—S2—C24—C23	−90.47 (14)	S1—C7—C12—C11	174.06 (12)
O3—S2—C25—C26	90.62 (14)	C8—C7—C12—N1	178.84 (17)
O3—S2—C25—C30	−81.60 (16)	C8—C7—C12—C11	−0.2 (3)
C24—S2—C25—C26	−159.91 (13)	C12—C7—C8—C9	0.6 (3)
C24—S2—C25—C30	27.87 (16)	C7—C8—C9—C10	−0.5 (3)
C25—S2—C24—C19	−27.36 (16)	C8—C9—C10—C11	0.1 (4)
C25—S2—C24—C23	159.69 (12)	C9—C10—C11—C12	0.3 (3)
C1—N1—C12—C7	−23.1 (3)	C10—C11—C12—N1	−179.29 (17)
C1—N1—C12—C11	155.82 (15)	C10—C11—C12—C7	−0.3 (3)
C12—N1—C1—C2	−158.65 (15)	N2—C19—C20—C21	−179.84 (15)
C12—N1—C1—C6	20.3 (3)	N2—C19—C24—S2	7.7 (3)
C1—N1—C13—C14	−82.95 (19)	N2—C19—C24—C23	−179.71 (15)
C13—N1—C1—C2	7.7 (3)	C20—C19—C24—S2	−172.93 (15)
C13—N1—C1—C6	−173.35 (14)	C20—C19—C24—C23	−0.4 (3)
C12—N1—C13—C14	83.93 (19)	C24—C19—C20—C21	0.8 (3)
C13—N1—C12—C7	170.51 (14)	C19—C20—C21—C22	−0.4 (3)
C13—N1—C12—C11	−10.5 (3)	C20—C21—C22—C23	−0.6 (3)
C19—N2—C30—C25	−19.6 (3)	C21—C22—C23—C24	1.0 (3)
C19—N2—C30—C29	159.75 (15)	C22—C23—C24—S2	172.62 (16)
C30—N2—C19—C20	−159.11 (15)	C22—C23—C24—C19	−0.5 (3)
C30—N2—C19—C24	20.2 (3)	S2—C25—C26—C27	−171.30 (13)
C19—N2—C31—C32	−79.65 (19)	S2—C25—C30—N2	−8.9 (3)
C31—N2—C19—C20	10.0 (3)	S2—C25—C30—C29	171.77 (12)
C31—N2—C19—C24	−170.65 (15)	C26—C25—C30—N2	179.37 (16)
C30—N2—C31—C32	89.82 (19)	C26—C25—C30—C29	−0.0 (3)
C31—N2—C30—C25	171.34 (15)	C30—C25—C26—C27	1.1 (3)
C31—N2—C30—C29	−9.3 (3)	C25—C26—C27—C28	−1.1 (3)
N1—C1—C2—C3	176.43 (15)	C26—C27—C28—C29	−0.0 (3)
N1—C1—C6—S1	12.3 (3)	C27—C28—C29—C30	1.1 (3)
N1—C1—C6—C5	−175.40 (14)	C28—C29—C30—N2	179.52 (17)
C2—C1—C6—S1	−168.70 (14)	C28—C29—C30—C25	−1.1 (3)

Hydrogen-bond geometry (Å, º) top

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)

Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₃NO₂S
M_r	307.37
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	93
a, b, c (Å)	16.797 (5), 10.197 (3), 17.664 (5)
β (°)	94.934 (5)
V (Å³)	3014.3 (15)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.15 × 0.15 × 0.05

Data collection
Diffractometer	Rigaku Saturn724+
Absorption correction	Numerical (NUMABS; Rigaku, 1999)
T_min, T_max	0.969, 0.989
No. of measured, independent and observed [F² > 2σ(F²)] reflections	24445, 6932, 5523
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.135, 1.08
No. of reflections	6931
No. of parameters	404
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.88, −0.47

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), CrystalStructure (Rigaku, 2010).

Hydrogen-bond geometry (Å, º) top

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)

Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+1/2.

Acknowledgements

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

References

Chu, S. S. C., de Meester, P., Jovanovic, M. V. & Biehl, E. R. (1985). Acta Cryst. C41, 1111–1114. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Dahl, S. G., Hjorth, M. & Hough, E. (1982). Mol. Pharmacol. 21, 409–414. CAS PubMed Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Gilman, H. & Ranck, R. O. (1958). J. Org. Chem. 23, 1903–1906. CrossRef CAS Google Scholar
Hough, E., Hjorth, M. & Dahl, S. G. (1982). Acta Cryst. B38, 2424–2428. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Hough, E., Hjorth, M. & Dahl, S. G. (1985a). Acta Cryst. C41, 383–386. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Hough, E., Wold, E. & Dahl, S. G. (1985b). Acta Cryst. C41, 386–389. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Jin, R.-F., Yu, K., Yang, S.-Y. & Huang, R.-B. (2010). Acta Cryst. E66, o3267. Web of Science CSD CrossRef IUCr Journals Google Scholar
Jovanovic, M. V., de Meester, P., Biehl, E. R. & Chu, S. S. C. (1986). J. Heterocycl. Chem. 23, 801–807. CrossRef CAS Google Scholar
Okuno, T., Ikeda, S., Kubo, N. & Sandman, D. J. (2006). Mol. Cryst. Liq. Cryst. 456, 35–44. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (1999). NUMABS. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2010). CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, Q., Yang, L., Xu, Z. & Sun, Y. (2009). Acta Cryst. E65, o1978. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xu, Z., Sun, Y., Yang, L. & Wang, Q. (2009). Acta Cryst. E65, o1799. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zaugg, H. E., Sweett, L. R. & Stone, G. R. (1958). J. Org. Chem. 23, 1389–1390. CrossRef CAS Web of Science Google Scholar