Transannular S...N inter­actions in 10-ethynyl-10H-pheno­thia­zine 5-oxide and 5,5-dioxide

The title compounds, C₁₄H₉NOS, (1), and C₁₄H₉NO₂S, (2), are oxidation products of the parent compound 10-ethynyl-10H-pheno­thia­zine. They differ with respect to transannular inter­actions, the intra­molecular S...N contact being shorter in (2). Inter­molecular Csp—H...O hydrogen bonds were detected in both crystals, and (1) was found to form stronger hydrogen bonds. These results are in agreement with the lower acidity of Csp—H in (2), caused by an increase in π-electron density due to the transannular S...N inter­action.

S1. Introduction

Pheno­thia­zines are known to be good electron donors and have attracted inter­est from the aspects of photoinduced electron transfer and magnetism (Sun et al., 2004; Okamoto et al., 2004; Okada et al., 1996). The pheno­thia­zine derivative 10-(prop-1-yn-1-yl)-10H-pheno­thia­zine, which incorporates an ynamine moiety, is well known as the first ynamine compound (Zaugg et al., 1958), and its structure has recently been reported (Umezono & Okuno, 2012). In 10-(prop-1-yn-1-yl)-10H-pheno­thia­zines, the effect of oxidation at the S atom was shown to extend towards a terminal methyl group through an acetyl­ene unit and was explained with a transannular inter­action (Umezono & Okuno, 2013). Despite the presence of a polar substituent such as sulfoxide or sulfone, however, no relevant inter­molecular contacts could be detected. In order to clearly demonstrate the transannular effect on the acetyl­ene unit, we prepared and structurally characterized 10-ethynyl-10H-pheno­thia­zines with a terminal H atom instead of a methyl group at the peripheral acetyl­ene. In this paper, we report the structures of 10-ethynyl-10H-pheno­thia­zine 5-oxide, (1), and 10-ethynyl-10H-pheno­thia­zine 5,5-dioxide, (2), and discuss their differences with respect to inter­molecular inter­actions as a consequence of transannular S···N inter­action. We have not been able to grow single crystals of the low-melting unsubstituted parent compound 10-ethynyl-10H-pheno­thia­zine.

S2. Experimental

S2.1. Synthesis and crystallization

Single crystals of (1) and (2) of sufficient quality for X-ray analysis were obtained by concentrating solutions of the compounds in di­chloro­methane. Compound (1) was prepared by mcpba oxidation of 10-ethynyl-10H-pheno­thia­zine as follows: to a solution of 10-ethynyl-10H-pheno­thia­zine (1.00 g, 4.48 mmol) in CH₂Cl₂ (100 ml), 3-chloro­perbenzoic acid (mcpba; 1.07 g, 4.03 mmol) was added at 233 K and the solution was stirred for 1 h. It was then poured into water and washed with aqueous NaHCO₃. The organic layer was dried over Na₂SO₄ and concentrated under reduced pressure. The residue was purified by gel-permeation chromatography to give colorless crystals of (1) (yield 0.90 g, 93%).

¹H NMR (CDCl₃): δ 7.95 (dd, J = 8.5, 0.8 Hz, 2H), 7.92 (dd, J = 7.8, 1.5 Hz, 2H), 7.64 (dt, J = 8.0, 1.6 Hz, 2H), 7.35 (dt, J = 7.5, 1.1 Hz, 2H), 3.60 (s, 1H). Compound (2) was prepared according to the published procedure of Okuno et al. (2006).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Csp-bound H atoms were located in difference Fourier maps and refined isotropically without any restrictions. The remaining H atoms were refined as riding on their parent C atoms, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C).

S3. Results and discussion

In 10-ethynyl-10H-pheno­thia­zine 5-oxide, (1), the pheno­thia­zine moiety has a butterfly structure as shown in Fig. 1; the two benzene rings subtend a dihedral angle of 149.66 (8)°. The central six-membered ring adopts a boat conformation in which the transannular S1···N1 distance is 3.090 (2) Å. The coordination around atom N1 is slightly pyramidal (Table 2), with the distance of N1 to the C1/C12/C13 plane of 0.113 (2) Å. These structural features of (1) are in good agreement with those in compounds reported earlier (Okuno et al., 2006; Umezono & Okuno, 2013). The acetyl­enic H atom is involved in an inter­molecular Csp—H···O hydrogen bond (Table 3). Several examples of close Csp—H···O contacts have been documented (Allen et al., 1996; Aurora et al., 2006; Howard et al., 1979; Kariuki et al., 1997; Lovas et al., 1977; Makal & Wozniak, 2009; Murty & Vasella, 2001; Souweha et al., 2007; Steiner et al., 1997; Yamauchi et al., 2007). The hydrogen bond in (1) can be classified as rather strong; it generates a helix along the a axis. Between neighbouring helices, π–π stacking inter­actions are recognized as shown in Fig. 2, with a C1···C8ⁱⁱⁱ distance of 3.337 (3) Å and a C8···C8^iv distance of 3.321 (3) Å [symmetry codes: (iii) -x+2, y, -z+3/2; (iv) -x+1, y, -z+3/2]. The centroid–centroid distances are 4.637 and 4.209 Å [between which types of rings?].

In 10-ethynyl-10H-pheno­thia­zine 5,5-dioxide, (2), the asymmetric unit comprises half a molecule; a mirror plane passes through the S atom, the ynamine fragment and the acetyl­enic H atom. The pheno­thia­zine moiety adopts a butterfly structure (Fig. 3), with a dihedral angle of 142.67 (10)° between the C1–C6 and C1ⁱ–C6ⁱ benzene rings [symmetry code: (i) x, -y+1/2, z], which is slightly smaller than in previously reported compounds. The central six-membered ring again is in boat conformation, with a shorter transannular S1···N1 distance of 2.967 (3) Å. Atom N1 is also pyramidal (Table 4), with a distance of 0.098 (3) Å to the C1/C1ⁱ/C7 plane. The acetyl­enic H atom is engaged in an inter­molecular Csp—H···O hydrogen bond (Table 5). This contact gives rise to a chain along the a axis, with π–π inter­actions between the chains as depicted in Fig. 4 and a distance between atoms C8 and C1^iv or C1^v of 3.391 (4) Å [symmetry codes: (iv) x+1/2, -y+1/2, -z+1/2; (v) x+1/2, y, -z+1/2].

The central six-membered rings in boat conformations correspond to the usual geometry for pheno­thia­zine 5-oxides and 5,5-dioxides, except for a few examples (Kormos et al., 2012). When one or both benzene rings are removed or replaced by a heteroaromatic ring, however, the resulting 1,4-thia­zine 5,5-dioxides are planar (Akkurt et al., 2005; Andreetti et al., 1974; Baraza­rte et al., 2008, 2009; Charris et al., 2007; Chia et al., 2008; Fraenkel et al., 1986; Girard et al., 1987; Wang, Mudraboyina et al., 2010; Wang, Wisner & Jennings, 2010) because ofeffective conjugation between the aromatic systems. Compound (2) shows a shorter transannular S···N contact than (1), indicating a stronger inter­action. As a result, (2) is thought to have a smaller dihedral angle than (1) or the compounds reported earlier.

As for inter­molecular contacts, the hydrogen-bonding pattern differs significantly. Almost linear hydrogen bonds are formed in (1), with a tendency towards a longer Csp—H bond. The H···O separation of 2.13 (3) Å is shorter than average Csp—H···O hydrogen-bond distances. On the other hand, the hydrogen bond in (2) is considered to be weaker. In the IR spectrum, a higher value for ν_C—H (3394 cm^-1) was observed in (2) than in (1) (3151 cm^-1), also suggesting that the hydrogen bond in (2) is weaker than that in (1). This weakening of the inter­molecular hydrogen bond in (2) can be explained by the transannular S···N inter­action in the pheno­thia­zine unit (Umezono & Okuno, 2013). The higher oxidation state in (2) results in a more positive charge on the S atom, thus enhancing the inter­action between S and the transannular N-atom donor. This inter­action also induces a more negative charge on the N atom and hence a higher π-electron density on the acetyl­ene group of (2) and lower acidity of the Csp—H atom. In ¹H NMR spectroscopy, this is reflected in a high field shift of the Csp—H with respect to the situation in (1).

In summary, we succeeded in a structural comparison of (1) and (2), both with terminal H atoms at the acetyl­ene moiety. The relatively short intra­molecular S···N distance results in a significant transannular inter­action in (2). Inter­molecular Csp—H···O hydrogen bonds were encountered in both structures, and stronger hydrogen bonds were found in (1). The increase in π-electron density, originating from the transannular S···N inter­action, is consistent with a decrease in the acidity of the Csp—H group in (2).

Related literature

For related literature, see: Akkurt et al. (2005); Allen et al. (1996); Andreetti et al. (1974); Aurora et al. (2006); Barazarte et al. (2008); Charris et al. (2007); Chia et al. (2008); Fraenkel et al. (1986); Girard et al. (1987); Howard et al. (1979); Kariuki et al. (1997); Kormos et al. (2012); Lovas et al. (1977); Makal & Wozniak (2009); Murty & Vasella (2001); Okada et al. (1996); Okamoto et al. (2004); Okuno et al. (2006); Souweha et al. (2007); Steiner et al. (1997); Sun et al. (2004); Umezono & Okuno (2012, 2013); Wang, Hong-Bo, Mudraboyina, Li, Jiaxin & Wisner (2010); Wang, Hong-Bo, Wisner & Jennings (2010); Yamauchi et al. (2007).

Computing details

For both compounds, data collection: CrystalClear (Rigaku, 2008). Cell refinement: CrystalClear (Rigaku, 2008) for (2). For both compounds, data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).

Figures

	Fig. 1. The molecular structure of (1), showing the 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 intermolecular interactions in (1). [Symmetry codes: (i) x+1/2, -y+1/2, -z+1; (ii) x-1/2, -y+1/2, -z+1; (iii) -x+2, y, -z+3/2; (iv) -x+1, y, -z+3/2.]
	Fig. 3. The molecular structure of (2), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres. [Symmetry code: (i) x, -y+1/2, z.]
	Fig. 4. A view of the intermolecular interactions in (2). [Symmetry codes: (i) x, -y+1/2, z; (ii) x+1, y, z; (iii) x-1, y, z; (iv) x+1/2, -y+1/2, -z+1/2; (v) x+1/2, y, -z+1/2; (vi) x-1/2, -y+1/2, -z+1/2.]

(1) 10-Ethynyl-10H-phenothiazine 5-oxide

Crystal data

C14H9NOS	F(000) = 992.00
Mr = 239.29	Dx = 1.452 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2n 2ab	Cell parameters from 5559 reflections
a = 7.9006 (19) Å	θ = 2.4–31.1°
b = 16.302 (4) Å	µ = 0.27 mm^−1
c = 16.998 (5) Å	T = 93 K
V = 2189.3 (10) Å^3	Block, colorless
Z = 8	0.10 × 0.05 × 0.05 mm

Data collection

Rigaku Saturn724+ diffractometer	2029 reflections with F^2 > 2σ(F^2)
Detector resolution: 28.445 pixels mm^-1	Rint = 0.063
ω scans	θmax = 27.5°
Absorption correction: numerical (NUMABS; Rigaku, 1999)	h = −10→8
Tmin = 0.980, Tmax = 0.986	k = −21→15
16927 measured reflections	l = −22→22
2516 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0798P)^2 + 0.6466P] where P = (Fo^2 + 2Fc^2)/3
2515 reflections	(Δ/σ)max < 0.001
158 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.47 e Å^−3
Primary atom site location: structure-invariant direct methods

Special details

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections except for one 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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.75165 (6)	0.06008 (3)	0.68675 (3)	0.01792 (19)
O1	0.61110 (19)	0.05632 (9)	0.62728 (9)	0.0231 (4)
N1	0.9343 (3)	0.19889 (11)	0.59667 (11)	0.0194 (4)
C1	1.0078 (3)	0.11984 (13)	0.59044 (12)	0.0188 (5)
C2	1.1464 (3)	0.10709 (14)	0.54108 (13)	0.0227 (5)
C3	1.2235 (3)	0.03169 (15)	0.53857 (13)	0.0241 (5)
C4	1.1651 (3)	−0.03340 (14)	0.58384 (13)	0.0244 (5)
C5	1.0252 (3)	−0.02186 (13)	0.63138 (13)	0.0225 (5)
C6	0.9441 (3)	0.05471 (12)	0.63481 (12)	0.0183 (5)
C7	0.7718 (3)	0.16400 (14)	0.71501 (13)	0.0188 (5)
C8	0.6956 (3)	0.18743 (13)	0.78573 (13)	0.0203 (5)
C9	0.6888 (3)	0.26913 (14)	0.80688 (13)	0.0227 (5)
C10	0.7554 (3)	0.32764 (14)	0.75571 (14)	0.0230 (5)
C11	0.8311 (3)	0.30590 (13)	0.68552 (13)	0.0216 (5)
C12	0.8446 (3)	0.22317 (13)	0.66499 (12)	0.0179 (5)
C13	0.9856 (3)	0.25802 (13)	0.54515 (13)	0.0208 (5)
C14	1.0316 (3)	0.30852 (14)	0.49945 (14)	0.0249 (5)
H2	1.1874	0.1506	0.5092	0.0273*
H3	1.3186	0.0239	0.5052	0.0289*
H4	1.2206	−0.0851	0.5821	0.0293*
H5	0.9834	−0.0662	0.6620	0.0270*
H8	0.6482	0.1470	0.8194	0.0244*
H9	0.6396	0.2852	0.8555	0.0272*
H10	0.7485	0.3840	0.7695	0.0276*
H11	0.8739	0.3471	0.6513	0.0259*
H14	1.064 (4)	0.3513 (16)	0.4587 (17)	0.032 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0149 (3)	0.0209 (4)	0.0180 (3)	0.00059 (19)	−0.00005 (18)	0.00298 (18)
O1	0.0173 (8)	0.0290 (9)	0.0229 (9)	−0.0014 (6)	−0.0040 (6)	−0.0004 (6)
N1	0.0170 (9)	0.0244 (10)	0.0167 (9)	0.0000 (7)	0.0014 (7)	0.0033 (7)
C1	0.0157 (10)	0.0234 (12)	0.0173 (10)	0.0012 (8)	−0.0027 (8)	−0.0024 (8)
C2	0.0182 (11)	0.0316 (13)	0.0184 (10)	−0.0025 (9)	0.0000 (9)	−0.0018 (9)
C3	0.0171 (11)	0.0353 (14)	0.0199 (11)	0.0030 (10)	−0.0005 (8)	−0.0050 (10)
C4	0.0204 (12)	0.0255 (12)	0.0273 (12)	0.0047 (9)	−0.0030 (9)	−0.0043 (9)
C5	0.0206 (11)	0.0250 (12)	0.0220 (11)	0.0003 (9)	−0.0030 (9)	−0.0001 (9)
C6	0.0159 (11)	0.0232 (11)	0.0156 (10)	−0.0005 (8)	−0.0010 (8)	−0.0012 (8)
C7	0.0150 (10)	0.0231 (12)	0.0183 (11)	0.0001 (9)	−0.0018 (8)	0.0016 (9)
C8	0.0132 (10)	0.0280 (13)	0.0199 (11)	0.0018 (9)	−0.0010 (9)	0.0034 (8)
C9	0.0174 (11)	0.0299 (13)	0.0209 (11)	0.0038 (9)	0.0018 (9)	−0.0028 (9)
C10	0.0193 (12)	0.0243 (12)	0.0254 (12)	0.0026 (9)	0.0007 (9)	−0.0012 (9)
C11	0.0172 (12)	0.0242 (13)	0.0233 (12)	−0.0013 (9)	−0.0026 (9)	0.0035 (9)
C12	0.0107 (10)	0.0251 (12)	0.0180 (10)	0.0015 (8)	0.0002 (8)	0.0011 (8)
C13	0.0164 (11)	0.0261 (12)	0.0199 (11)	0.0008 (9)	−0.0022 (8)	−0.0010 (9)
C14	0.0195 (12)	0.0308 (14)	0.0245 (12)	−0.0000 (9)	0.0019 (9)	0.0022 (10)

Geometric parameters (Å, º)

S1—O1	1.5029 (17)	C8—C9	1.381 (4)
S1—C6	1.760 (3)	C9—C10	1.394 (4)
S1—C7	1.768 (3)	C10—C11	1.381 (4)
N1—C1	1.417 (3)	C11—C12	1.397 (3)
N1—C12	1.417 (3)	C13—C14	1.189 (4)
N1—C13	1.364 (3)	C2—H2	0.950
C1—C2	1.395 (3)	C3—H3	0.950
C1—C6	1.396 (3)	C4—H4	0.950
C2—C3	1.373 (4)	C5—H5	0.950
C3—C4	1.390 (4)	C8—H8	0.950
C4—C5	1.382 (4)	C9—H9	0.950
C5—C6	1.404 (3)	C10—H10	0.950
C7—C8	1.398 (4)	C11—H11	0.950
C7—C12	1.408 (3)	C14—H14	1.02 (3)
O1—S1—C6	107.38 (10)	C10—C11—C12	119.8 (2)
O1—S1—C7	106.76 (10)	N1—C12—C7	120.50 (19)
C6—S1—C7	96.09 (10)	N1—C12—C11	120.83 (19)
C1—N1—C12	121.35 (18)	C7—C12—C11	118.6 (2)
C1—N1—C13	118.21 (18)	N1—C13—C14	178.9 (3)
C12—N1—C13	118.52 (18)	C1—C2—H2	119.979
N1—C1—C2	120.13 (19)	C3—C2—H2	119.983
N1—C1—C6	120.21 (19)	C2—C3—H3	119.360
C2—C1—C6	119.6 (2)	C4—C3—H3	119.360
C1—C2—C3	120.0 (2)	C3—C4—H4	120.481
C2—C3—C4	121.3 (2)	C5—C4—H4	120.484
C3—C4—C5	119.0 (2)	C4—C5—H5	119.659
C4—C5—C6	120.7 (2)	C6—C5—H5	119.667
S1—C6—C1	123.00 (16)	C7—C8—H8	119.865
S1—C6—C5	117.33 (16)	C9—C8—H8	119.851
C1—C6—C5	119.3 (2)	C8—C9—H9	120.547
S1—C7—C8	117.17 (17)	C10—C9—H9	120.567
S1—C7—C12	121.94 (17)	C9—C10—H10	119.093
C8—C7—C12	120.5 (2)	C11—C10—H10	119.108
C7—C8—C9	120.3 (2)	C10—C11—H11	120.109
C8—C9—C10	118.9 (2)	C12—C11—H11	120.118
C9—C10—C11	121.8 (2)	C13—C14—H14	176.5 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O1^i	1.02 (3)	2.13 (3)	3.145 (3)	175 (2)

Symmetry code: (i) x+1/2, −y+1/2, −z+1.

(2) 10-Ethynyl-10H-phenothiazine 5,5-dioxide

Crystal data

C14H9NO2S	F(000) = 528.00
Mr = 255.29	Dx = 1.482 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ac 2n	Cell parameters from 3716 reflections
a = 9.177 (3) Å	θ = 2.2–31.4°
b = 11.520 (4) Å	µ = 0.27 mm^−1
c = 10.819 (3) Å	T = 93 K
V = 1143.8 (7) Å^3	Block, colorless
Z = 4	0.10 × 0.10 × 0.10 mm

Data collection

Rigaku Saturn724+ diffractometer	1297 reflections with F^2 > 2σ(F^2)
Detector resolution: 28.445 pixels mm^-1	Rint = 0.050
ω scans	θmax = 27.5°
Absorption correction: numerical (NUMABS; Rigaku, 1999)	h = −11→11
Tmin = 0.958, Tmax = 0.973	k = −14→14
8777 measured reflections	l = −14→13
1375 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0558P)^2 + 1.1593P] where P = (Fo^2 + 2Fc^2)/3
1375 reflections	(Δ/σ)max < 0.001
94 parameters	Δρmax = 0.84 e Å^−3
0 restraints	Δρmin = −0.49 e Å^−3
Primary atom site location: structure-invariant direct methods

Special details

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. 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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.23021 (7)	0.2500	−0.03905 (6)	0.0258 (3)
O1	0.3021 (2)	0.2500	−0.15688 (18)	0.0301 (5)
O2	0.0733 (2)	0.2500	−0.0386 (2)	0.0401 (6)
N1	0.5097 (3)	0.2500	0.0988 (2)	0.0243 (5)
C1	0.4337 (3)	0.14262 (17)	0.10106 (16)	0.0245 (4)
C2	0.4924 (3)	0.04626 (19)	0.16022 (18)	0.0318 (5)
C3	0.4104 (3)	−0.05549 (18)	0.1686 (2)	0.0382 (6)
C4	0.2723 (3)	−0.06268 (19)	0.1188 (3)	0.0377 (6)
C5	0.2150 (3)	0.0317 (2)	0.0571 (2)	0.0334 (5)
C6	0.2959 (3)	0.13401 (17)	0.04785 (17)	0.0241 (4)
C7	0.6558 (3)	0.2500	0.1211 (3)	0.0289 (7)
C8	0.7830 (4)	0.2500	0.1366 (3)	0.0363 (7)
H2	0.5876	0.0496	0.1947	0.0382*
H3	0.4505	−0.1211	0.2094	0.0458*
H4	0.2171	−0.1320	0.1269	0.0452*
H5	0.1208	0.0271	0.0210	0.0401*
H8	0.885 (5)	0.2500	0.136 (4)	0.037 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0264 (4)	0.0263 (4)	0.0246 (4)	0.0000	−0.0009 (3)	0.0000
O1	0.0395 (12)	0.0311 (11)	0.0196 (10)	0.0000	−0.0018 (9)	0.0000
O2	0.0252 (11)	0.0451 (14)	0.0501 (15)	0.0000	−0.0021 (10)	0.0000
N1	0.0263 (11)	0.0256 (12)	0.0211 (11)	0.0000	−0.0006 (9)	0.0000
C1	0.0339 (10)	0.0224 (9)	0.0171 (8)	0.0008 (8)	0.0065 (7)	−0.0010 (7)
C2	0.0425 (12)	0.0323 (11)	0.0206 (9)	0.0094 (9)	0.0073 (8)	0.0025 (8)
C3	0.0642 (15)	0.0219 (10)	0.0285 (10)	0.0098 (10)	0.0194 (11)	0.0055 (8)
C4	0.0569 (15)	0.0218 (11)	0.0343 (11)	−0.0049 (10)	0.0196 (10)	−0.0023 (9)
C5	0.0417 (12)	0.0281 (11)	0.0304 (10)	−0.0084 (9)	0.0117 (9)	−0.0048 (9)
C6	0.0310 (10)	0.0223 (9)	0.0190 (9)	−0.0001 (8)	0.0059 (7)	−0.0014 (7)
C7	0.0328 (15)	0.0372 (16)	0.0167 (12)	0.0000	−0.0019 (11)	0.0000
C8	0.0331 (17)	0.049 (2)	0.0269 (15)	0.0000	−0.0045 (13)	0.0000

Geometric parameters (Å, º)

S1—O1	1.435 (2)	C3—C4	1.379 (4)
S1—O2	1.440 (2)	C4—C5	1.380 (4)
S1—C6	1.742 (2)	C5—C6	1.397 (3)
S1—C6^i	1.742 (2)	C7—C8	1.179 (5)
N1—C1	1.420 (3)	C2—H2	0.950
N1—C1^i	1.420 (3)	C3—H3	0.950
N1—C7	1.362 (4)	C4—H4	0.950
C1—C2	1.390 (3)	C5—H5	0.950
C1—C6	1.393 (3)	C8—H8	0.94 (4)
C2—C3	1.396 (4)
O1—S1—O2	117.56 (13)	C4—C5—C6	119.8 (3)
O1—S1—C6	108.68 (9)	S1—C6—C1	118.87 (15)
O1—S1—C6^i	108.68 (9)	S1—C6—C5	120.13 (16)
O2—S1—C6	110.14 (9)	C1—C6—C5	120.88 (19)
O2—S1—C6^i	110.14 (9)	N1—C7—C8	178.0 (4)
C6—S1—C6^i	100.22 (10)	C1—C2—H2	120.282
C1—N1—C1^i	121.2 (3)	C3—C2—H2	120.288
C1—N1—C7	118.69 (13)	C2—C3—H3	119.316
C1^i—N1—C7	118.69 (13)	C4—C3—H3	119.316
N1—C1—C2	120.9 (2)	C3—C4—H4	120.264
N1—C1—C6	120.04 (19)	C5—C4—H4	120.266
C2—C1—C6	119.03 (19)	C4—C5—H5	120.116
C1—C2—C3	119.4 (2)	C6—C5—H5	120.110
C2—C3—C4	121.4 (2)	C7—C8—H8	172 (3)
C3—C4—C5	119.5 (3)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O2^ii	0.94 (4)	2.56 (4)	3.270 (5)	133 (3)

Symmetry code: (ii) x+1, y, z.