Crystal structures of (N-methyl-N-phenyl-amino)(N-methyl-N-phenyl-carbamoyl)sulfide and the corresponding disulfane.

The title compounds, (N-methyl-N-phenyl-amino)(N-methyl-N-phenyl-car-bam-oyl)sulfide, C15H16N2OS, (I), and (N-methyl-N-phenyl-amino)-(N-methyl-N-phenyl-carbamo-yl)disulfane, C15H16N2OS2, (II), are stable derivatives of (chloro-carbon-yl)sulfenyl chloride and (chloro-carbon-yl)disulfanyl chloride, respectively. The torsion angle about the S-S bond in (II) is -92.62 (6)°, which is close to the theoretical value of 90°. In the crystal of (II), non-classical inter-molecular C-H⋯O hydrogen bonds form centrosymmetric cyclic dimers [graph set R 2 (2)(10)], while inter-dimer C-H⋯S inter-actions generate chains extending along the b axis.

Chemical context

As part of a multifaceted program in synthetic and mechanistic organosulfur chemistry (Barany et al., 1983 ▸; Barany & Mott, 1984 ▸; Schroll & Barany, 1986 ▸; Schrader et al., 2011 ▸, and references cited therein), we frequently encounter challenging-to-characterize compounds with one or more reactive acid chloride and/or sulfenyl chloride moieties. These are converted to the corresponding stable carbamoyl and/or sulfenamide derivatives, which are often crystalline, through their reliable, rapid, and high-yield reactions with N-methyl­aniline.

The present paper reports the structures of two such derivatives, i.e. (N-methyl-N-phenyl­amino)(N-methyl-N-phenyl­car­bamoyl)sulfide (I) and (N-methyl-N-phenyl­amino)(N-methyl-N-phenyl­carbamo­yl)­disulfane (II), as determined by X-ray crystallography. The title compounds are derived respectively from (chloro­carbon­yl)sulfenyl chloride and (chloro­carbon­yl)disulfanyl chloride, which are noxious, distillable liquids. They are the first two members of a general family of compounds with the structure Ph(Me)N(C=O)SN(Me)Ph, in which the higher members (n = 3–6) were found, but not isolated in crystalline form, as components in the reactions of in situ generated (2-propoxydi­chloro­meth­yl)(chloro­carbon­yl)polysulfanes with N-methyl­aniline (Schroll & Barany, 1986 ▸).

Structural commentary

The title compounds differ by the number of sulfur atoms: one in (I) (Fig. 1 ▸) versus two in (II) (Fig. 2 ▸), and by the resulting relative orientations of the Ph(Me)N(C=O)S and N(Me)Ph moieties. Otherwise, they share similar bond lengths and angles across all analogous bonds (Table 1 ▸). Furthermore, the mol­ecular parameters are all within expected ranges. The S—S bond of (II) is 2.0625 (5) Å, which is comparable to the bond length in elemental sulfur, S8 (2.07 Å), but slightly longer than the 2.03 Å found for bis­(N-methyl-N-phenyl­carbamo­yl)di­sul­fane ([Ph(Me)N(C=O)S]2) (III) (Schroll et al., 2012 ▸). In compound (III) (Fig. 3 ▸), the slight shortening of the S—S bond was attributed to a partial double-bond character imparted by the adjacent carbonyl groups. Because (II) is essentially (III) minus one carbonyl group, it is not surprising for the S—S bond length in (II) to be closer to that in S8. The torsion angle about the S—S bond in (II) is −92.62 (6)°, which is comparable to the theoretical optimum of 90° (Pauling, 1949 ▸; Torrico-Vallejos et al., 2010 ▸).

Figure 1

The mol­ecular conformation of compound (I), showing 50% probability displacement ellipsoids with all non-H atoms labeled and numbered.

Figure 2

The mol­ecular conformation of compound (II), showing 50% probability displacement ellipsoids with all non-hydrogen atoms labeled and numbered.

Table 1

Selected geometric parameters for compounds (I) and (II) (Å, °)

Note that when S is not numbered, it is S1 for compound (I) and S2 for compound (II). To specify certain torsion angles, the last atom in the linear structure differs between the two compounds, so X is used in place of an atom label.

	(I)	(II)
N1—C8	1.351 (3)	1.357 (2)
S—N2	1.678 (2)	1.666 (1)
S1—C8	1.824 (2)	1.827 (1)
S1—S2	–	2.0625 (5)
C9—N2—S	115.90 (14)	116.23 (8)
C10—N2—S	118.74 (12)	118.86 (8)
C10—N2—C9	118.37 (17)	118.17 (11)
C1—N1—C8—S1	3.3 (2)	9.16 (15)
N1—C8—S1—X	172.19 (14)	−165.53 (8)
C8—S1—S2—N2	–	−92.62 (6)
C10—N2—S—X	77.3 (2)	−72.86 (10)

Figure 3

Structures of selected comparison compounds, bis­(N-methyl-N-phenyl­carbamo­yl)disulfane, (III), and bis­(N-methyl-N-phenyl­amino)­tris­ulfane, (IV)

Supra­molecular features

The unit cell of (I) contains two mol­ecules related by a twofold screw axis (Fig. 4 ▸). There are no inter­molecular contacts in the crystal structure of (I). In the crystal of (II) non-classical inter­molecular C7—H⋯O1 hydrogen bonds (Table 2 ▸) form centrosymmetric cyclic dimers [graph set (10)]. Chains of mol­ecules extending along the b axis result from inter-dimer C2—H⋯S1 inter­actions (Fig. 5 ▸).

Figure 4

Crystal packing of (I). H atoms are not shown.

Table 2

Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯S1i	0.95	2.84	3.766 (1)	165
C7—H7B⋯O1ii	0.98	2.60	3.532 (2)	160

Symmetry codes: (i) ; (ii) .

Figure 5

Crystal packing of (II). Only H atoms involved in inter­molecular C2—H⋯S1 and C7—H⋯O1=C8 non-classical hydrogen bonds are shown.

Database survey

A search for similar structures in the Cambridge Structural Database (CSD; Version 5.36, update of November 2014; Groom & Allen, 2014 ▸) gave bis­(N-methyl-N-phenyl­car­bam­o­yl)di­sulfane (III), published previously from our research (Schroll et al., 2012 ▸), as well as two similar bis(car­bamoyl)disulfanes (Bereman et al., 1983 ▸; Li et al., 2006 ▸). Structures containing a similar sulfenamide moiety were absent from the CSD, although two structures reported N—S bonds connected to ‘imido’ [(RC=O)2N] moieties (Farrell et al., 2002 ▸; Ul-Haque & Behforouz, 1976 ▸). A very recent report from our research describes bis­(N-methyl-N-phenyl­amino)­tris­ulfane (IV) (Fig. 3 ▸) (Barany et al., 2015 ▸), an N-methyl­anilide which contains two ‘sulfenamide’ ends [whereas (III) contains two ‘carbamo­yl’ ends]. Not surprisingly, many geometric parameters of (III) and (IV) superimpose onto the corresponding portions of (I) and (II). For example, the sulfenamide N2—S bond lengths of (I) [1.6784 (15) Å] and (II) [1.6660 (11) Å] are close to that of (IV) [average N—S bond length of 1.657 Å] and the carbamoyl N1—C8 and S1—C8 bond lengths of (I) [1.351 (3) and 1.824 (2) Å, respectively] and (II) [1.357 (2) and 1.827 (1) Å, respectively] are similar to that of (III) [1.345 (3) and 1.825 (2) Å, respectively]. In addition, the torsion angles about the N1—C8 bond of (I) [3.3 (2)°] and (II) [9.16 (15)°] are similar to that of (III) [−6.4 (3)°] and the torsion angle about the N2—S bond in (I) [77.3 (2)°] and (II) [−72.86 (10)] are similar but slightly smaller than that of (IV) (average angle 80.3°).

Synthesis and crystallization

The title compound (I) was prepared on scales of up to 0.1 mol by addition of a 0.5 M solution of (chloro­carbon­yl)sulfenyl chloride in CHCl3 to an equal volume of a 2 M solution of N-methyl­aniline in CHCl3 at 273 K, followed by stirring for 30 min at 298 K (Barany et al., 1983 ▸). Workup by washing with equal volumes of 1 N aqueous HCl (3×) and brine (once), drying (MgSO4), filtering, and concentrating in vacuo gave the product as an oil (nominally qu­anti­tative), and recrystallization from hot hexa­nes (30 mL g−1) gave a white solid (typically 65–80% recovery), m.p. 338–340 K, which was stable for several decades when stored under ambient conditions. 1H NMR (300 MHz; CDCl3): δ 7.43–7.48 (m, 3H), 7.37 (dd, J = 1.9, 7.9 Hz, 2H), 7.23–7.29 (m, 2H), 7.12 (dd, J = 1.0, 8.8 Hz, 2H), 6.86 (t, J = 7.2 Hz, 1H), 3.41 (s, 3H), 3.31 (s, 3H). X-ray quality crystals were obtained by dissolving (I) (100 mg) in minimal CHCl3 (200 µL) and then adding hexane (2 mL), followed by slow evaporation of the solvent at 298 K over two days.

To prepare compound (II), a solution of (chloro­carbon­yl)disulfanyl chloride (Schroll & Barany, 1986 ▸) (814 mg, 5.0 mmol) in CH2Cl2 (15 mL) was added over 10 min to a stirred solution of N-methyl­aniline (2.2 mL, 20 mmol) in CH2Cl2 (11 mL) at 273 K. The homogeneous reaction mixture was allowed to warm to 298 K, stirred an additional 30 min, and standard extractive workup [compare to procedure above for (I)] gave the product as a brown oil (1.44 g, 94% crude yield). The crude product was purified by flash column chromatography, eluting with hexa­ne–ethyl acetate (8:1), to provide a yellow oil (1.37 g), which after storing under hexa­nes at 253 K overnight produced the title product as an off-white solid (757 mg, 2.5 mmol, 50%), m.p. 326–327 K (lit. 325–327 K; Barany & Mott, 1984 ▸). 1H NMR (300 MHz; CDCl3): δ 7.36–7.41 (m, 3H), 7.2–7.3 (m, 6H), 6.9–7.0 (m, 1H), 3.40 (s, 3H), 3.37 (s, 3H). X-ray quality crystals were prepared by dissolving (II) (23 mg) in CH2Cl2 (100 µL) and then adding heptane (200 µL), followed by slow evaporation of the solvent at 278 K over 11 days.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. Hydrogen atoms were included at calculated positions [C—H(aromatic) = 0.95 Å or C—H(meth­yl) = 0.98 Å] and treated as riding, with U isoH = 1.2U eqC(aromatic) or 1.5U eqC(meth­yl). With (I), although of no importance in this achiral mol­ecule, the Flack absolute structure factor (Parsons et al., 2013 ▸) was determined as 0.05 (3) for 1450 Friedel pairs.

Table 3

Experimental details

	(I)	(II)
Crystal data
Chemical formula	C15H16N2OS	C15H16N2OS2
M r	272.36	304.42
Crystal system, space group	Monoclinic, P21	Monoclinic, P21/c
Temperature (K)	173	123
a, b, c (Å)	9.0682 (7), 6.8402 (5), 11.4686 (9)	16.0414 (17), 5.5023 (6), 17.2986 (19)
β (°)	103.349 (1)	105.564 (1)
V (Å3)	692.16 (9)	1470.9 (3)
Z	2	4
Radiation type	Mo Kα	Mo Kα
μ (mm−1)	0.23	0.36
Crystal size (mm)	0.40 × 0.35 × 0.12	0.41 × 0.18 × 0.12
Data collection
Diffractometer	Bruker SMART APEXII	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2002 ▸)	Multi-scan (SADABS; Bruker, 2002 ▸)
T min, T max	0.687, 0.746	0.699, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	8061, 3145, 2961	16044, 3355, 3033
R int	0.022	0.024
(sin θ/λ)max (Å−1)	0.648	0.649
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.027, 0.067, 1.05	0.028, 0.070, 1.06
No. of reflections	3145	3355
No. of parameters	174	183
No. of restraints	1	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.19, −0.15	0.32, −0.22
Absolute structure	Flack x determined using 1285 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸)	–
Absolute structure parameter	0.05 (3)	–

Computer programs: APEX2 and SAINT (Bruker, 2002 ▸), SHELXS97 and SHELXTL (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸) and Mercury (Macrae et al., 2008 ▸).

Crystal structure: contains datablock(s) I, II, 1. DOI: 10.1107/S2056989015018289/zs2342sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015018289/zs2342Isup4.hkl

Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989015018289/zs2342IIsup5.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015018289/zs2342Isup4.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015018289/zs2342IIsup5.cml

CCDC references: 1428652, 1428651

Additional supporting information: crystallographic information; 3D view; checkCIF report

C15H16N2OS	F(000) = 288
Mr = 272.36	Dx = 1.307 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 9.0682 (7) Å	Cell parameters from 2915 reflections
b = 6.8402 (5) Å	θ = 2.3–27.4°
c = 11.4686 (9) Å	µ = 0.23 mm−1
β = 103.349 (1)°	T = 173 K
V = 692.16 (9) Å3	Plate, colourless
Z = 2	0.40 × 0.35 × 0.12 mm

Bruker SMART APEXII diffractometer	2961 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.022
Absorption correction: multi-scan (SADABS; Bruker, 2002)	θmax = 27.4°, θmin = 1.8°
Tmin = 0.687, Tmax = 0.746	h = −11→11
8061 measured reflections	k = −8→8
3145 independent reflections	l = −14→14

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.027	w = 1/[σ2(Fo2) + (0.0297P)2 + 0.1164P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.067	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.19 e Å−3
3145 reflections	Δρmin = −0.15 e Å−3
174 parameters	Absolute structure: Flack x determined using 1285 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.05 (3)

Geometry. All e.s.d.'s are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

	x	y	z	Uiso*/Ueq
S1	0.32124 (5)	0.41906 (8)	0.67886 (4)	0.02848 (13)
O1	0.41605 (17)	0.0518 (2)	0.71103 (13)	0.0314 (3)
N1	0.2797 (2)	0.1212 (3)	0.52292 (15)	0.0265 (4)
N2	0.39549 (17)	0.4094 (3)	0.82703 (13)	0.0264 (3)
C1	0.2020 (2)	0.2644 (3)	0.43921 (17)	0.0248 (4)
C2	0.2834 (2)	0.3936 (4)	0.38553 (17)	0.0289 (5)
H2A	0.3910	0.3938	0.4080	0.035*
C3	0.2080 (3)	0.5227 (3)	0.2990 (2)	0.0352 (5)
H3A	0.2637	0.6114	0.2619	0.042*
C4	0.0517 (3)	0.5218 (4)	0.2669 (2)	0.0383 (6)
H4A	−0.0001	0.6109	0.2079	0.046*
C5	−0.0302 (2)	0.3922 (4)	0.31988 (19)	0.0391 (6)
H5A	−0.1378	0.3926	0.2972	0.047*
C6	0.0446 (2)	0.2620 (4)	0.40601 (19)	0.0317 (5)
H6A	−0.0112	0.1719	0.4420	0.038*
C7	0.2839 (2)	−0.0795 (4)	0.47987 (18)	0.0317 (4)
H7A	0.3168	−0.1675	0.5483	0.048*
H7B	0.3553	−0.0877	0.4276	0.048*
H7C	0.1826	−0.1176	0.4348	0.048*
C8	0.3469 (2)	0.1659 (3)	0.63758 (18)	0.0247 (4)
C9	0.3038 (3)	0.3084 (4)	0.8984 (2)	0.0330 (5)
H9A	0.3380	0.3467	0.9827	0.050*
H9B	0.3151	0.1668	0.8911	0.050*
H9C	0.1970	0.3443	0.8691	0.050*
C10	0.5557 (2)	0.4074 (4)	0.86869 (15)	0.0248 (4)
C11	0.6441 (3)	0.5337 (4)	0.81829 (18)	0.0317 (5)
H11A	0.5971	0.6177	0.7545	0.038*
C12	0.8000 (3)	0.5379 (4)	0.8604 (2)	0.0364 (5)
H12A	0.8592	0.6238	0.8248	0.044*
C13	0.8703 (2)	0.4179 (5)	0.95412 (18)	0.0363 (5)
H13A	0.9774	0.4200	0.9825	0.044*
C14	0.7824 (3)	0.2954 (4)	1.0056 (2)	0.0357 (5)
H14A	0.8297	0.2139	1.0706	0.043*
C15	0.6264 (3)	0.2891 (3)	0.9641 (2)	0.0306 (5)
H15A	0.5676	0.2041	1.0008	0.037*

	U11	U22	U33	U12	U13	U23
S1	0.0321 (2)	0.0234 (2)	0.0263 (2)	0.0027 (2)	−0.00070 (17)	−0.0012 (2)
O1	0.0339 (8)	0.0284 (8)	0.0284 (8)	0.0061 (6)	0.0002 (6)	0.0003 (7)
N1	0.0291 (9)	0.0245 (9)	0.0240 (8)	−0.0005 (7)	0.0019 (7)	−0.0019 (7)
N2	0.0278 (8)	0.0279 (8)	0.0232 (7)	−0.0030 (9)	0.0053 (6)	−0.0007 (9)
C1	0.0266 (10)	0.0259 (10)	0.0207 (10)	0.0016 (8)	0.0031 (8)	−0.0037 (8)
C2	0.0283 (10)	0.0291 (13)	0.0273 (9)	−0.0012 (9)	0.0021 (8)	−0.0029 (9)
C3	0.0461 (13)	0.0285 (12)	0.0294 (11)	−0.0029 (10)	0.0054 (10)	−0.0002 (9)
C4	0.0475 (14)	0.0365 (13)	0.0268 (11)	0.0149 (11)	−0.0002 (10)	0.0002 (10)
C5	0.0275 (10)	0.0534 (17)	0.0340 (11)	0.0107 (12)	0.0024 (8)	−0.0059 (12)
C6	0.0253 (10)	0.0419 (13)	0.0285 (11)	0.0011 (9)	0.0075 (8)	−0.0026 (9)
C7	0.0364 (10)	0.0276 (9)	0.0309 (10)	0.0006 (12)	0.0073 (8)	−0.0040 (12)
C8	0.0222 (9)	0.0231 (10)	0.0287 (10)	−0.0003 (8)	0.0059 (8)	−0.0021 (8)
C9	0.0323 (11)	0.0330 (12)	0.0355 (12)	−0.0054 (10)	0.0115 (9)	−0.0031 (10)
C10	0.0292 (9)	0.0252 (9)	0.0197 (8)	−0.0028 (10)	0.0049 (7)	−0.0053 (9)
C11	0.0363 (11)	0.0364 (12)	0.0218 (10)	−0.0061 (10)	0.0055 (9)	0.0016 (9)
C12	0.0351 (12)	0.0457 (14)	0.0302 (11)	−0.0135 (11)	0.0115 (10)	−0.0034 (10)
C13	0.0286 (10)	0.0442 (12)	0.0348 (10)	−0.0034 (13)	0.0045 (8)	−0.0094 (14)
C14	0.0363 (12)	0.0343 (11)	0.0322 (12)	0.0010 (10)	−0.0007 (9)	0.0006 (10)
C15	0.0345 (11)	0.0261 (10)	0.0307 (11)	−0.0027 (10)	0.0069 (9)	0.0017 (9)

S1—N2	1.6784 (15)	C6—H6A	0.9500
S1—C8	1.824 (2)	C7—H7A	0.9800
O1—C8	1.212 (3)	C7—H7B	0.9800
N1—C8	1.351 (3)	C7—H7C	0.9800
N1—C1	1.437 (3)	C9—H9A	0.9800
N1—C7	1.462 (3)	C9—H9B	0.9800
N2—C10	1.421 (2)	C9—H9C	0.9800
N2—C9	1.467 (3)	C10—C11	1.392 (3)
C1—C2	1.383 (3)	C10—C15	1.393 (3)
C1—C6	1.390 (3)	C11—C12	1.385 (3)
C2—C3	1.385 (3)	C11—H11A	0.9500
C2—H2A	0.9500	C12—C13	1.385 (4)
C3—C4	1.380 (3)	C12—H12A	0.9500
C3—H3A	0.9500	C13—C14	1.379 (4)
C4—C5	1.384 (4)	C13—H13A	0.9500
C4—H4A	0.9500	C14—C15	1.385 (3)
C5—C6	1.386 (3)	C14—H14A	0.9500
C5—H5A	0.9500	C15—H15A	0.9500
N2—S1—C8	100.36 (10)	H7A—C7—H7C	109.5
C8—N1—C1	122.48 (18)	H7B—C7—H7C	109.5
C8—N1—C7	120.04 (17)	O1—C8—N1	125.12 (19)
C1—N1—C7	117.48 (16)	O1—C8—S1	120.52 (16)
C10—N2—C9	118.37 (17)	N1—C8—S1	114.34 (15)
C10—N2—S1	118.74 (12)	N2—C9—H9A	109.5
C9—N2—S1	115.90 (14)	N2—C9—H9B	109.5
C2—C1—C6	120.34 (19)	H9A—C9—H9B	109.5
C2—C1—N1	120.23 (18)	N2—C9—H9C	109.5
C6—C1—N1	119.25 (19)	H9A—C9—H9C	109.5
C1—C2—C3	120.05 (19)	H9B—C9—H9C	109.5
C1—C2—H2A	120.0	C11—C10—C15	118.84 (18)
C3—C2—H2A	120.0	C11—C10—N2	119.8 (2)
C4—C3—C2	119.7 (2)	C15—C10—N2	121.28 (19)
C4—C3—H3A	120.2	C12—C11—C10	120.5 (2)
C2—C3—H3A	120.2	C12—C11—H11A	119.8
C3—C4—C5	120.5 (2)	C10—C11—H11A	119.8
C3—C4—H4A	119.7	C11—C12—C13	120.6 (2)
C5—C4—H4A	119.7	C11—C12—H12A	119.7
C4—C5—C6	120.1 (2)	C13—C12—H12A	119.7
C4—C5—H5A	120.0	C14—C13—C12	118.91 (19)
C6—C5—H5A	120.0	C14—C13—H13A	120.5
C5—C6—C1	119.4 (2)	C12—C13—H13A	120.5
C5—C6—H6A	120.3	C13—C14—C15	121.1 (2)
C1—C6—H6A	120.3	C13—C14—H14A	119.4
N1—C7—H7A	109.5	C15—C14—H14A	119.4
N1—C7—H7B	109.5	C14—C15—C10	120.0 (2)
H7A—C7—H7B	109.5	C14—C15—H15A	120.0
N1—C7—H7C	109.5	C10—C15—H15A	120.0
C8—S1—N2—C10	77.3 (2)	C1—N1—C8—S1	3.3 (2)
C8—S1—N2—C9	−73.05 (18)	C7—N1—C8—S1	−176.52 (14)
C8—N1—C1—C2	78.2 (3)	N2—S1—C8—O1	−6.02 (19)
C7—N1—C1—C2	−101.9 (2)	N2—S1—C8—N1	172.19 (14)
C8—N1—C1—C6	−106.6 (2)	C9—N2—C10—C11	−166.6 (2)
C7—N1—C1—C6	73.2 (2)	S1—N2—C10—C11	43.8 (3)
C6—C1—C2—C3	0.6 (3)	C9—N2—C10—C15	9.7 (3)
N1—C1—C2—C3	175.69 (19)	S1—N2—C10—C15	−139.90 (19)
C1—C2—C3—C4	0.1 (3)	C15—C10—C11—C12	1.6 (3)
C2—C3—C4—C5	−0.4 (3)	N2—C10—C11—C12	178.0 (2)
C3—C4—C5—C6	0.0 (4)	C10—C11—C12—C13	−0.6 (4)
C4—C5—C6—C1	0.6 (3)	C11—C12—C13—C14	−0.6 (4)
C2—C1—C6—C5	−0.9 (3)	C12—C13—C14—C15	0.8 (4)
N1—C1—C6—C5	−176.1 (2)	C13—C14—C15—C10	0.2 (4)
C1—N1—C8—O1	−178.6 (2)	C11—C10—C15—C14	−1.4 (3)
C7—N1—C8—O1	1.6 (3)	N2—C10—C15—C14	−177.7 (2)

C15H16N2OS2	F(000) = 640
Mr = 304.42	Dx = 1.375 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.0414 (17) Å	Cell parameters from 2950 reflections
b = 5.5023 (6) Å	θ = 3.1–27.5°
c = 17.2986 (19) Å	µ = 0.36 mm−1
β = 105.564 (1)°	T = 123 K
V = 1470.9 (3) Å3	Block, colorless
Z = 4	0.41 × 0.18 × 0.12 mm

Bruker APEXII CCD diffractometer	3033 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.024
φ and ω scans	θmax = 27.5°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −20→20
Tmin = 0.699, Tmax = 0.746	k = −7→7
16044 measured reflections	l = −22→22
3355 independent reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028	H-atom parameters constrained
wR(F2) = 0.070	w = 1/[σ2(Fo2) + (0.0301P)2 + 0.7728P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
3355 reflections	Δρmax = 0.32 e Å−3
183 parameters	Δρmin = −0.22 e Å−3

Geometry. All e.s.d.'s are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

	x	y	z	Uiso*/Ueq
S1	0.24264 (2)	0.27366 (6)	0.12829 (2)	0.01720 (9)
S2	0.27516 (2)	0.52421 (6)	0.05260 (2)	0.01821 (9)
O1	0.15803 (6)	0.07736 (18)	−0.01294 (5)	0.0215 (2)
N1	0.12052 (7)	−0.0673 (2)	0.09646 (6)	0.0173 (2)
N2	0.36329 (7)	0.4255 (2)	0.02877 (6)	0.0184 (2)
C1	0.12310 (8)	−0.0405 (2)	0.18005 (7)	0.0160 (2)
C2	0.16345 (8)	−0.2156 (2)	0.23508 (8)	0.0199 (3)
H2A	0.1907	−0.3512	0.2182	0.024*
C3	0.16379 (9)	−0.1914 (3)	0.31517 (8)	0.0232 (3)
H3A	0.1907	−0.3119	0.3530	0.028*
C4	0.12493 (9)	0.0083 (3)	0.33984 (8)	0.0227 (3)
H4A	0.1266	0.0268	0.3948	0.027*
C5	0.08363 (9)	0.1808 (3)	0.28448 (8)	0.0239 (3)
H5A	0.0565	0.3166	0.3015	0.029*
C6	0.08171 (8)	0.1558 (2)	0.20413 (8)	0.0209 (3)
H6A	0.0523	0.2721	0.1659	0.025*
C7	0.06129 (8)	−0.2499 (2)	0.05015 (8)	0.0204 (3)
H7A	0.0626	−0.2431	−0.0061	0.031*
H7B	0.0024	−0.2168	0.0537	0.031*
H7C	0.0792	−0.4118	0.0719	0.031*
C8	0.16585 (8)	0.0771 (2)	0.05874 (7)	0.0163 (2)
C9	0.34991 (9)	0.2336 (3)	−0.03205 (8)	0.0233 (3)
H9A	0.3968	0.2384	−0.0585	0.035*
H9B	0.2943	0.2589	−0.0720	0.035*
H9C	0.3497	0.0750	−0.0063	0.035*
C10	0.44464 (8)	0.4352 (2)	0.08806 (7)	0.0168 (2)
C11	0.50700 (9)	0.2568 (2)	0.09139 (8)	0.0219 (3)
H11A	0.4951	0.1250	0.0546	0.026*
C12	0.58679 (9)	0.2706 (3)	0.14843 (9)	0.0256 (3)
H12A	0.6291	0.1485	0.1500	0.031*
C13	0.60500 (9)	0.4600 (3)	0.20266 (8)	0.0242 (3)
H13A	0.6594	0.4686	0.2416	0.029*
C14	0.54283 (9)	0.6379 (3)	0.19970 (8)	0.0228 (3)
H14A	0.5548	0.7683	0.2371	0.027*
C15	0.46357 (9)	0.6273 (2)	0.14279 (8)	0.0202 (3)
H15A	0.4219	0.7512	0.1410	0.024*

	U11	U22	U33	U12	U13	U23
S1	0.01726 (16)	0.01986 (16)	0.01529 (15)	−0.00238 (11)	0.00576 (12)	−0.00051 (11)
S2	0.01769 (16)	0.01601 (16)	0.02234 (16)	0.00171 (11)	0.00784 (12)	0.00252 (12)
O1	0.0234 (5)	0.0262 (5)	0.0148 (4)	−0.0021 (4)	0.0049 (4)	0.0012 (4)
N1	0.0179 (5)	0.0187 (5)	0.0158 (5)	−0.0033 (4)	0.0055 (4)	−0.0012 (4)
N2	0.0170 (5)	0.0226 (6)	0.0175 (5)	−0.0012 (4)	0.0079 (4)	−0.0021 (4)
C1	0.0150 (6)	0.0183 (6)	0.0159 (6)	−0.0029 (5)	0.0063 (4)	−0.0013 (5)
C2	0.0203 (6)	0.0192 (6)	0.0208 (6)	0.0021 (5)	0.0066 (5)	−0.0011 (5)
C3	0.0234 (7)	0.0254 (7)	0.0192 (6)	0.0008 (5)	0.0030 (5)	0.0033 (5)
C4	0.0231 (7)	0.0293 (7)	0.0177 (6)	−0.0064 (5)	0.0088 (5)	−0.0050 (5)
C5	0.0269 (7)	0.0203 (7)	0.0299 (7)	−0.0006 (5)	0.0168 (6)	−0.0042 (5)
C6	0.0211 (6)	0.0193 (6)	0.0251 (7)	0.0025 (5)	0.0110 (5)	0.0037 (5)
C7	0.0197 (6)	0.0204 (6)	0.0198 (6)	−0.0034 (5)	0.0031 (5)	−0.0009 (5)
C8	0.0144 (6)	0.0161 (6)	0.0181 (6)	0.0020 (5)	0.0039 (5)	0.0013 (5)
C9	0.0211 (6)	0.0322 (8)	0.0173 (6)	−0.0031 (5)	0.0064 (5)	−0.0068 (5)
C10	0.0177 (6)	0.0185 (6)	0.0165 (6)	−0.0035 (5)	0.0087 (5)	0.0004 (5)
C11	0.0235 (7)	0.0204 (7)	0.0225 (6)	−0.0008 (5)	0.0074 (5)	−0.0064 (5)
C12	0.0212 (7)	0.0255 (7)	0.0295 (7)	0.0026 (5)	0.0056 (6)	−0.0049 (6)
C13	0.0198 (6)	0.0292 (7)	0.0228 (7)	−0.0040 (5)	0.0042 (5)	−0.0027 (6)
C14	0.0264 (7)	0.0220 (7)	0.0218 (6)	−0.0060 (5)	0.0098 (5)	−0.0069 (5)
C15	0.0226 (6)	0.0177 (6)	0.0230 (6)	−0.0014 (5)	0.0106 (5)	−0.0023 (5)

S1—C8	1.8273 (13)	C6—H6A	0.9500
S1—S2	2.0625 (5)	C7—H7A	0.9800
S2—N2	1.6660 (11)	C7—H7B	0.9800
O1—C8	1.2123 (15)	C7—H7C	0.9800
N1—C8	1.3569 (16)	C9—H9A	0.9800
N1—C1	1.4429 (15)	C9—H9B	0.9800
N1—C7	1.4646 (16)	C9—H9C	0.9800
N2—C10	1.4281 (16)	C10—C11	1.3917 (18)
N2—C9	1.4656 (16)	C10—C15	1.3967 (18)
C1—C2	1.3865 (18)	C11—C12	1.3929 (19)
C1—C6	1.3888 (18)	C11—H11A	0.9500
C2—C3	1.3905 (18)	C12—C13	1.3800 (19)
C2—H2A	0.9500	C12—H12A	0.9500
C3—C4	1.386 (2)	C13—C14	1.388 (2)
C3—H3A	0.9500	C13—H13A	0.9500
C4—C5	1.384 (2)	C14—C15	1.3847 (19)
C4—H4A	0.9500	C14—H14A	0.9500
C5—C6	1.3888 (18)	C15—H15A	0.9500
C5—H5A	0.9500
C8—S1—S2	102.60 (4)	H7A—C7—H7C	109.5
N2—S2—S1	108.37 (4)	H7B—C7—H7C	109.5
C8—N1—C1	123.17 (10)	O1—C8—N1	124.80 (12)
C8—N1—C7	119.43 (10)	O1—C8—S1	122.64 (10)
C1—N1—C7	117.28 (10)	N1—C8—S1	112.55 (9)
C10—N2—C9	118.17 (11)	N2—C9—H9A	109.5
C10—N2—S2	118.86 (8)	N2—C9—H9B	109.5
C9—N2—S2	116.23 (8)	H9A—C9—H9B	109.5
C2—C1—C6	120.47 (11)	N2—C9—H9C	109.5
C2—C1—N1	119.97 (11)	H9A—C9—H9C	109.5
C6—C1—N1	119.51 (11)	H9B—C9—H9C	109.5
C1—C2—C3	119.60 (12)	C11—C10—C15	118.84 (12)
C1—C2—H2A	120.2	C11—C10—N2	120.77 (11)
C3—C2—H2A	120.2	C15—C10—N2	120.38 (12)
C4—C3—C2	120.05 (13)	C10—C11—C12	120.30 (12)
C4—C3—H3A	120.0	C10—C11—H11A	119.8
C2—C3—H3A	120.0	C12—C11—H11A	119.8
C5—C4—C3	120.12 (12)	C13—C12—C11	120.62 (13)
C5—C4—H4A	119.9	C13—C12—H12A	119.7
C3—C4—H4A	119.9	C11—C12—H12A	119.7
C4—C5—C6	120.16 (12)	C12—C13—C14	119.24 (13)
C4—C5—H5A	119.9	C12—C13—H13A	120.4
C6—C5—H5A	119.9	C14—C13—H13A	120.4
C1—C6—C5	119.55 (12)	C15—C14—C13	120.65 (12)
C1—C6—H6A	120.2	C15—C14—H14A	119.7
C5—C6—H6A	120.2	C13—C14—H14A	119.7
N1—C7—H7A	109.5	C14—C15—C10	120.34 (12)
N1—C7—H7B	109.5	C14—C15—H15A	119.8
H7A—C7—H7B	109.5	C10—C15—H15A	119.8
N1—C7—H7C	109.5
S1—S2—N2—C10	−72.86 (10)	C7—N1—C8—S1	−175.04 (9)
S1—S2—N2—C9	77.90 (9)	C8—S1—S2—N2	−92.62 (6)
C8—N1—C1—C2	−110.35 (14)	S2—S1—C8—O1	15.13 (12)
C7—N1—C1—C2	73.77 (15)	S2—S1—C8—N1	−165.53 (8)
C8—N1—C1—C6	72.46 (16)	C9—N2—C10—C11	−4.59 (17)
C7—N1—C1—C6	−103.41 (14)	S2—N2—C10—C11	145.60 (11)
C6—C1—C2—C3	−1.25 (19)	C9—N2—C10—C15	174.12 (11)
N1—C1—C2—C3	−178.41 (12)	S2—N2—C10—C15	−35.69 (15)
C1—C2—C3—C4	−0.8 (2)	C15—C10—C11—C12	−0.02 (19)
C2—C3—C4—C5	1.8 (2)	N2—C10—C11—C12	178.70 (12)
C3—C4—C5—C6	−0.6 (2)	C10—C11—C12—C13	0.4 (2)
C2—C1—C6—C5	2.36 (19)	C11—C12—C13—C14	−0.2 (2)
N1—C1—C6—C5	179.54 (12)	C12—C13—C14—C15	−0.4 (2)
C4—C5—C6—C1	−1.4 (2)	C13—C14—C15—C10	0.8 (2)
C1—N1—C8—O1	−171.52 (12)	C11—C10—C15—C14	−0.56 (19)
C7—N1—C8—O1	4.27 (19)	N2—C10—C15—C14	−179.29 (11)
C1—N1—C8—S1	9.16 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···S1i	0.95	2.84	3.766 (1)	165
C7—H7B···O1ii	0.98	2.60	3.532 (2)	160