2-[2-(Benzyl­sulfan­yl)phen­yl]-1,1,3,3-tetra­methyl­guanidine

Neuba, A.; Flörke, U.; Henkel, G.

doi:10.1107/S1600536811014577

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Pages o1202-o1203

doi:10.1107/S1600536811014577

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2-[2-(Benzylsulfanyl)phenyl]-1,1,3,3-tetramethylguanidine

Adam Neuba,^a Ulrich Flörke ^a ^* and Gerald Henkel ^a

^aDepartment Chemie, Fakultät für Naturwissenschaften, Universität Paderborn, Warburgerstrasse 100, D-33098 Paderborn, Germany
^*Correspondence e-mail: ulrich.floerke@upb.de

(Received 15 April 2011; accepted 18 April 2011; online 22 April 2011)

The molecular structure of the title compound, C₁₈H₂₃N₃S, shows it to be a derivative of an aminothiophenol possessing a tetramethylguanidine group with a localized C=N double bond of 1.304 (2) Å and a protected thiol functional group as an S-benzyl thioether. The two aromatic ring planes make a dihedral angle of 67.69 (6)°.

Related literature

For synthesis, see: Neuba (2009 ); Lindoy & Livingstone (1968 ); Herres-Pawlis et al. (2005 ). For related structures, see: Neuba et al. (2007a ,b ,c ); Herres et al. (2004 ); Raab et al. (2003 , 2002 ); Peters et al. (2008 ). For complexes of metal centres with bis(tetramethylguanidino)propylene and amine guanidine hybrids, see: Harmjanz (1997 ); Waden (1999 ); Pohl et al. (2000 ); Schneider (2000 ); Wittmann (1999 ); Wittmann et al. (2001 ); Herres et al. (2005 ); Herres-Pawlis et al. (2009 ); Börner et al. (2007 , 2009 ). For sulfur guanidine hybrids based on aminothiophenol and cysteamine, see: Neuba (2009); Neuba et al. (2008a ,b , 2010 , 2011 ).

Experimental

Crystal data

C₁₈H₂₃N₃S
M_r = 313.45
Monoclinic, P 2₁ /c
a = 7.869 (2) Å
b = 26.850 (7) Å
c = 8.314 (2) Å
β = 106.959 (5)°
V = 1680.2 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 120 K
0.42 × 0.33 × 0.29 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.923, T_max = 0.946
14278 measured reflections
3988 independent reflections
2816 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.091
S = 0.92
3988 reflections
203 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811014577/bt5518sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811014577/bt5518Isup2.hkl

checkCIF report

Comment top

The synthesis and characterization of novel molecules containing nitrogen and sulfur as donor functions and their application in synthesis of sulfur copper complexes is important for biomimetic copper–sulfur chemistry. In search of multifunctional ligands we have extended our studies to guanidyl-type systems with N-donor functions. The first derivative, the ligand bis(tetramethyl-guanidino)propylene as well as amine guanidine hybrids and their complexes with Cu, Fe, Ni, Ag, Mn, Co and Zn have recently been investigated (Harmjanz, 1997; Waden, 1999; Pohl et al., 2000; Schneider, 2000; Wittmann, 1999; Wittmann et al., 2001; Herres-Pawlis et al., 2005, 2009; Herres et al., 2005; Neuba et al., 2008a,b; 2010; Börner et al. 2007, 2009). We have now developed several sulfur guanidine hybrids based on aminothiophenol and cysteamine (Neuba et al., 2007a,b,c; Neuba, 2009). The synthesized sulfur guanidine compounds possess aliphatic and aromatic thioethers or disulfide groups and were used in the synthesis of copper thiolate complexes to mimic active centres like the Cu_A in cytochrome-c oxidase and N₂O-reductase (Neuba et al., 2011). The two aromatic ring planes make a dihedral angle of 67.69 (6)° and the N1—C6—C11—S1—C12—C13 moiety is mostly planar with largest deviation of 0.084 (1) Å for S1 from the best plane. The guanidine plane C1N₃ makes an angle of 59.80 (5)° with the attached aromatic ring. The N1═C1 guanidine double bond measures 1.304 (2) Å and is clearly localized. Similar double-bond localization is observed in other guanidine compounds (e.g. Herres et al., 2004; Neuba et al., 2007a,b; Raab et al., 2002, 2003; Peters et al., 2008).

Related literature top

For synthesis, see: Neuba (2009); ; Lindoy & Livingstone (1968); Herres-Pawlis et al. (2005). For related structures, see: Neuba et al. (2007a,b,c); Herres et al. (2004); Raab et al. (2003); Peters et al. (2008); Raab et al. (2002). For complexes of metal centres with bis(tetramethyl-guanidino)propylene and amine guanidine hybrids, see: Harmjanz (1997); Waden (1999); Pohl et al. (2000); Schneider (2000); Wittmann (1999); Wittmann et al. (2001); Herres et al. (2005); Herres-Pawlis et al. (2009); Börner et al. (2007, 2009). For sulfur guanidine hybrids based on aminothiophenol and cysteamine, see: Neuba (2009); Neuba et al. (2007a,b,c, 2008a,b, 2010, 2011).

Experimental top

The title compound was prepared as follows: a solution of tetramethylchloroformamidinium chlorid (Herres-Pawlis et al., 2005) (5.13 g, 30 mmol) in dry MeCN was added dropwise to an ice-cooled solution of 2-(benzylthio)aniline (Lindoy & Livingstone, 1968) (6.45 g, 30 mmol) and triethylamine (4.18 ml, 3.03 g, 30 mmol) in dry MeCN. After 3 h under reflux, a solution of NaOH (1.2 g, 30 mmol) in water was added. The solvents and NEt₃ were then evaporated under vacuum. In order to deprotonate the mono-hydrochloride, 50 wt% KOH (aqueous, 15 ml) was added and the free base was extracted into the MeCN phase (3 × 80 ml). The organic phase was dried with Na₂SO₄. After filtration, the solvent was evaporated under reduced pressure. The title compound was obtained as white powder (yield 69%, 6.4 g). Colourless crystals suitable for X-ray diffraction were obtained by slow cooling of a hot saturated MeCN solution.

Spectroscopic analysis: ¹H NMR (500 MHz, CDCl₃, 25°C, δ, p.p.m.): 2.68 (s, 12H, CH₃), 4.10 (s, 2H, CH₂), 6.59 (d, 1H, CH), 6.80 (t, 1H, CH), 7.03 (t, 1H, CH), 7.15 (d, 1H, CH), 7.21 (t, 1H, CH), 7.28 (t, 2H, CH), 7.36 (d, 2H, CH); ¹³C NMR (125 MHz, CDCl₃, 25°C, δ, p.p.m.): 37.3 (CH₂), 39.5 (CH₃), 120.5 (CH), 121.7 (CH), 126.1 (CH), 126.9 (CH), 127.2 (CH), 127.6 (CH), 128.4 (CH), 128.7 (C_quat), 129.1 (CH), 136.6 (C_quat), 137.8 (C_quat), 160.0 (C_gua); IR (KBr, ν, cm^-1): 3053 (w), 3030 (w), 3003 (w), 2918 (m), 2848 (m), 2790 (w), 1589 (vs (C═N)), 1558 (s (C═N)), 1500 (m (C═N)), 1460 (m), 1425 (m), 1377 (s), 1279 (w), 1232 (w), 1207 (w), 1144 (m), 1066 (m), 1038 (m), 1020 (s), 914 (w), 850 (w), 806 (vw), 777 (m), 715 (s), 696 (m), 682 (w), 621 (w), 571 (w), 545 (w), 498 (vw), 484 (w), 461 (w), 445 (w). EI–MS (m/z (%)): 313.0 (100) [M⁺], 280.0 (31), 269.1 (8) [M⁺ - N(CH₃)₂], 242.0 (5), 237.0 (10) [M⁺ - Ph], 222.0 (14) [M⁺ - CH₂Ph], 215.0 (20), 190.0 (12) [M⁺ - SCH₂Ph], 179.0 (76), 148.9 (28), 135.9 (20), 124.0 (9) [SCH₂Ph⁺], 91.0 (76), 72.0 (20).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures top

Fig. 1. Molecular structure with displacement ellipsoids drawn at the 50% probability level.

2-[2-(Benzylsulfanyl)phenyl]-1,1,3,3-tetramethylguanidine top

Crystal data top

C₁₈H₂₃N₃S	F(000) = 672
M_r = 313.45	D_x = 1.239 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 842 reflections
a = 7.869 (2) Å	θ = 2.7–27.7°
b = 26.850 (7) Å	µ = 0.19 mm⁻¹
c = 8.314 (2) Å	T = 120 K
β = 106.959 (5)°	Block, colourless
V = 1680.2 (8) Å³	0.42 × 0.33 × 0.29 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	3988 independent reflections
Radiation source: sealed tube	2816 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
ϕ and ω scans	θ_max = 27.9°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −10→9
T_min = 0.923, T_max = 0.946	k = −35→35
14278 measured reflections	l = −10→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: difference Fourier map
wR(F²) = 0.091	H-atom parameters constrained
S = 0.92	w = 1/[σ²(F_o²) + (0.0443P)²] where P = (F_o² + 2F_c²)/3
3988 reflections	(Δ/σ)_max = 0.001
203 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₈H₂₃N₃S	V = 1680.2 (8) Å³
M_r = 313.45	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.869 (2) Å	µ = 0.19 mm⁻¹
b = 26.850 (7) Å	T = 120 K
c = 8.314 (2) Å	0.42 × 0.33 × 0.29 mm
β = 106.959 (5)°

Data collection top

Bruker SMART APEX diffractometer	3988 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	2816 reflections with I > 2σ(I)
T_min = 0.923, T_max = 0.946	R_int = 0.066
14278 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 0.92	Δρ_max = 0.24 e Å⁻³
3988 reflections	Δρ_min = −0.34 e Å⁻³
203 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) 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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
S1	0.48274 (6)	0.392868 (13)	0.76377 (5)	0.02350 (11)
N1	0.64141 (18)	0.33140 (4)	0.56770 (16)	0.0214 (3)
N2	0.93294 (17)	0.29594 (4)	0.63993 (16)	0.0232 (3)
N3	0.68294 (18)	0.24922 (4)	0.50838 (17)	0.0239 (3)
C1	0.7516 (2)	0.29479 (5)	0.57258 (18)	0.0203 (3)
C2	1.0512 (2)	0.27118 (7)	0.5595 (2)	0.0362 (4)
H2A	0.9806	0.2524	0.4615	0.054*
H2B	1.1294	0.2483	0.6395	0.054*
H2C	1.1231	0.2961	0.5232	0.054*
C3	1.0191 (2)	0.33296 (6)	0.7646 (2)	0.0291 (4)
H3A	1.0587	0.3609	0.7089	0.044*
H3B	1.1220	0.3179	0.8466	0.044*
H3C	0.9349	0.3450	0.8225	0.044*
C4	0.4983 (2)	0.24676 (6)	0.4081 (2)	0.0311 (4)
H4A	0.4223	0.2445	0.4825	0.047*
H4B	0.4800	0.2173	0.3354	0.047*
H4C	0.4678	0.2768	0.3385	0.047*
C5	0.7491 (2)	0.20329 (5)	0.5999 (2)	0.0309 (4)
H5A	0.8732	0.2079	0.6666	0.046*
H5B	0.7414	0.1760	0.5196	0.046*
H5C	0.6772	0.1952	0.6746	0.046*
C6	0.6947 (2)	0.38116 (5)	0.56372 (19)	0.0192 (3)
C7	0.7988 (2)	0.39792 (5)	0.4653 (2)	0.0233 (3)
H7A	0.8470	0.3744	0.4052	0.028*
C8	0.8338 (2)	0.44823 (6)	0.4527 (2)	0.0252 (4)
H8A	0.9042	0.4589	0.3838	0.030*
C9	0.7656 (2)	0.48271 (5)	0.5412 (2)	0.0236 (3)
H9A	0.7905	0.5171	0.5343	0.028*
C10	0.6610 (2)	0.46705 (5)	0.63978 (19)	0.0220 (3)
H10A	0.6153	0.4908	0.7009	0.026*
C11	0.6223 (2)	0.41684 (5)	0.65010 (18)	0.0192 (3)
C12	0.4411 (2)	0.44748 (5)	0.8758 (2)	0.0243 (4)
H12A	0.5549	0.4615	0.9463	0.029*
H12B	0.3797	0.4733	0.7947	0.029*
C13	0.3272 (2)	0.43232 (5)	0.98479 (19)	0.0210 (3)
C14	0.4001 (2)	0.40508 (6)	1.1318 (2)	0.0274 (4)
H14A	0.5226	0.3966	1.1635	0.033*
C15	0.2967 (3)	0.39029 (6)	1.2317 (2)	0.0317 (4)
H15A	0.3480	0.3719	1.3316	0.038*
C16	0.1184 (3)	0.40237 (6)	1.1860 (2)	0.0332 (4)
H16A	0.0467	0.3919	1.2539	0.040*
C17	0.0442 (2)	0.42969 (6)	1.0417 (2)	0.0329 (4)
H17A	−0.0781	0.4384	1.0113	0.039*
C18	0.1484 (2)	0.44444 (6)	0.9414 (2)	0.0266 (4)
H18A	0.0967	0.4630	0.8420	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0297 (2)	0.01664 (17)	0.0296 (2)	−0.00079 (16)	0.01715 (18)	−0.00202 (15)
N1	0.0224 (7)	0.0167 (6)	0.0277 (7)	−0.0022 (5)	0.0116 (6)	−0.0044 (5)
N2	0.0206 (7)	0.0215 (6)	0.0263 (7)	−0.0002 (5)	0.0047 (6)	−0.0055 (5)
N3	0.0234 (7)	0.0164 (6)	0.0296 (7)	−0.0001 (5)	0.0043 (6)	−0.0045 (5)
C1	0.0237 (9)	0.0187 (7)	0.0199 (8)	−0.0011 (6)	0.0089 (7)	−0.0020 (6)
C2	0.0267 (10)	0.0419 (10)	0.0414 (11)	0.0044 (8)	0.0121 (9)	−0.0069 (8)
C3	0.0288 (10)	0.0255 (8)	0.0281 (9)	−0.0054 (7)	0.0008 (8)	−0.0025 (7)
C4	0.0253 (10)	0.0251 (8)	0.0400 (10)	−0.0031 (7)	0.0049 (8)	−0.0076 (7)
C5	0.0350 (10)	0.0193 (7)	0.0367 (10)	0.0001 (7)	0.0076 (9)	−0.0016 (7)
C6	0.0175 (8)	0.0181 (7)	0.0219 (8)	−0.0009 (6)	0.0058 (7)	−0.0018 (6)
C7	0.0221 (9)	0.0230 (8)	0.0277 (8)	0.0002 (6)	0.0119 (7)	−0.0037 (6)
C8	0.0228 (9)	0.0273 (8)	0.0279 (9)	−0.0026 (7)	0.0111 (7)	0.0035 (7)
C9	0.0242 (9)	0.0168 (7)	0.0289 (9)	−0.0020 (6)	0.0061 (7)	0.0020 (6)
C10	0.0228 (9)	0.0173 (7)	0.0252 (8)	0.0013 (6)	0.0059 (7)	−0.0012 (6)
C11	0.0182 (8)	0.0195 (7)	0.0209 (8)	−0.0004 (6)	0.0071 (7)	−0.0002 (6)
C12	0.0305 (10)	0.0174 (7)	0.0280 (9)	0.0022 (6)	0.0131 (8)	−0.0036 (6)
C13	0.0258 (9)	0.0169 (7)	0.0218 (8)	0.0007 (6)	0.0092 (7)	−0.0061 (6)
C14	0.0259 (9)	0.0296 (8)	0.0267 (9)	0.0056 (7)	0.0076 (8)	−0.0013 (7)
C15	0.0425 (11)	0.0296 (8)	0.0243 (9)	0.0015 (8)	0.0117 (8)	0.0015 (7)
C16	0.0423 (12)	0.0292 (9)	0.0372 (10)	−0.0078 (8)	0.0260 (9)	−0.0093 (7)
C17	0.0224 (10)	0.0332 (9)	0.0451 (11)	0.0010 (7)	0.0129 (9)	−0.0113 (8)
C18	0.0282 (10)	0.0235 (8)	0.0281 (9)	0.0028 (7)	0.0082 (8)	−0.0025 (6)

Geometric parameters (Å, º) top

S1—C11	1.7661 (15)	C6—C11	1.413 (2)
S1—C12	1.8175 (15)	C7—C8	1.389 (2)
N1—C1	1.3035 (19)	C7—H7A	0.9500
N1—C6	1.4033 (18)	C8—C9	1.384 (2)
N2—C1	1.373 (2)	C8—H8A	0.9500
N2—C3	1.4536 (19)	C9—C10	1.386 (2)
N2—C2	1.455 (2)	C9—H9A	0.9500
N3—C1	1.3804 (18)	C10—C11	1.390 (2)
N3—C4	1.451 (2)	C10—H10A	0.9500
N3—C5	1.4628 (19)	C12—C13	1.505 (2)
C2—H2A	0.9800	C12—H12A	0.9900
C2—H2B	0.9800	C12—H12B	0.9900
C2—H2C	0.9800	C13—C18	1.385 (2)
C3—H3A	0.9800	C13—C14	1.396 (2)
C3—H3B	0.9800	C14—C15	1.380 (2)
C3—H3C	0.9800	C14—H14A	0.9500
C4—H4A	0.9800	C15—C16	1.381 (3)
C4—H4B	0.9800	C15—H15A	0.9500
C4—H4C	0.9800	C16—C17	1.382 (2)
C5—H5A	0.9800	C16—H16A	0.9500
C5—H5B	0.9800	C17—C18	1.387 (2)
C5—H5C	0.9800	C17—H17A	0.9500
C6—C7	1.391 (2)	C18—H18A	0.9500

C11—S1—C12	102.33 (7)	C8—C7—H7A	119.2
C1—N1—C6	121.20 (13)	C6—C7—H7A	119.2
C1—N2—C3	121.30 (13)	C9—C8—C7	119.62 (14)
C1—N2—C2	122.01 (13)	C9—C8—H8A	120.2
C3—N2—C2	114.35 (14)	C7—C8—H8A	120.2
C1—N3—C4	118.43 (13)	C8—C9—C10	120.05 (14)
C1—N3—C5	120.43 (14)	C8—C9—H9A	120.0
C4—N3—C5	113.92 (13)	C10—C9—H9A	120.0
N1—C1—N2	126.77 (14)	C9—C10—C11	120.61 (14)
N1—C1—N3	118.33 (15)	C9—C10—H10A	119.7
N2—C1—N3	114.87 (13)	C11—C10—H10A	119.7
N2—C2—H2A	109.5	C10—C11—C6	119.88 (14)
N2—C2—H2B	109.5	C10—C11—S1	124.60 (12)
H2A—C2—H2B	109.5	C6—C11—S1	115.51 (11)
N2—C2—H2C	109.5	C13—C12—S1	108.58 (10)
H2A—C2—H2C	109.5	C13—C12—H12A	110.0
H2B—C2—H2C	109.5	S1—C12—H12A	110.0
N2—C3—H3A	109.5	C13—C12—H12B	110.0
N2—C3—H3B	109.5	S1—C12—H12B	110.0
H3A—C3—H3B	109.5	H12A—C12—H12B	108.4
N2—C3—H3C	109.5	C18—C13—C14	118.55 (15)
H3A—C3—H3C	109.5	C18—C13—C12	121.19 (14)
H3B—C3—H3C	109.5	C14—C13—C12	120.25 (15)
N3—C4—H4A	109.5	C15—C14—C13	120.91 (16)
N3—C4—H4B	109.5	C15—C14—H14A	119.5
H4A—C4—H4B	109.5	C13—C14—H14A	119.5
N3—C4—H4C	109.5	C14—C15—C16	119.81 (16)
H4A—C4—H4C	109.5	C14—C15—H15A	120.1
H4B—C4—H4C	109.5	C16—C15—H15A	120.1
N3—C5—H5A	109.5	C15—C16—C17	120.10 (16)
N3—C5—H5B	109.5	C15—C16—H16A	120.0
H5A—C5—H5B	109.5	C17—C16—H16A	120.0
N3—C5—H5C	109.5	C16—C17—C18	119.97 (17)
H5A—C5—H5C	109.5	C16—C17—H17A	120.0
H5B—C5—H5C	109.5	C18—C17—H17A	120.0
C7—C6—N1	123.59 (13)	C13—C18—C17	120.66 (16)
C7—C6—C11	118.26 (13)	C13—C18—H18A	119.7
N1—C6—C11	117.77 (13)	C17—C18—H18A	119.7
C8—C7—C6	121.54 (14)

C6—N1—C1—N2	28.2 (2)	C9—C10—C11—S1	−177.01 (12)
C6—N1—C1—N3	−153.64 (14)	C7—C6—C11—C10	−2.2 (2)
C3—N2—C1—N1	21.5 (2)	N1—C6—C11—C10	−175.37 (14)
C2—N2—C1—N1	−140.14 (17)	C7—C6—C11—S1	176.95 (12)
C3—N2—C1—N3	−156.70 (13)	N1—C6—C11—S1	3.76 (18)
C2—N2—C1—N3	41.6 (2)	C12—S1—C11—C10	−7.87 (16)
C4—N3—C1—N1	12.7 (2)	C12—S1—C11—C6	173.05 (12)
C5—N3—C1—N1	−135.83 (16)	C11—S1—C12—C13	−178.03 (11)
C4—N3—C1—N2	−168.95 (14)	S1—C12—C13—C18	−105.18 (15)
C5—N3—C1—N2	42.6 (2)	S1—C12—C13—C14	74.12 (16)
C1—N1—C6—C7	42.6 (2)	C18—C13—C14—C15	0.3 (2)
C1—N1—C6—C11	−144.63 (15)	C12—C13—C14—C15	−179.05 (14)
N1—C6—C7—C8	173.60 (15)	C13—C14—C15—C16	0.2 (2)
C11—C6—C7—C8	0.8 (2)	C14—C15—C16—C17	−0.8 (2)
C6—C7—C8—C9	0.7 (2)	C15—C16—C17—C18	0.9 (2)
C7—C8—C9—C10	−0.9 (2)	C14—C13—C18—C17	−0.2 (2)
C8—C9—C10—C11	−0.5 (2)	C12—C13—C18—C17	179.14 (14)
C9—C10—C11—C6	2.0 (2)	C16—C17—C18—C13	−0.4 (2)

Experimental details

Crystal data
Chemical formula	C₁₈H₂₃N₃S
M_r	313.45
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	7.869 (2), 26.850 (7), 8.314 (2)
β (°)	106.959 (5)
V (Å³)	1680.2 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.19
Crystal size (mm)	0.42 × 0.33 × 0.29

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.923, 0.946
No. of measured, independent and observed [I > 2σ(I)] reflections	14278, 3988, 2816
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.091, 0.92
No. of reflections	3988
No. of parameters	203
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.34

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXTL (Sheldrick, 2008) and local programs.

Acknowledgements

The authors thank the German Research Council (DFG) and the Federal Ministry of Education and Research (BMBF) for continuous support of their work. AN thanks the university of Paderborn for granting a doctorate scholarship.

References

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