2-[2-(Benzyl-sulfan-yl)phen-yl]-1,1,3,3-tetra-methyl-guanidine.

The mol-ecular structure of the title compound, C(18)H(23)N(3)S, shows it to be a derivative of an amino-thio-phenol possessing a tetra-methyl-guanidine group with a localized C=N double bond of 1.304 (2) Å and a protected thiol functional group as an S-benzyl thio-ether. 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 = 313.45

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.091

S = 0.92

3988 reflections

203 parameters

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −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.

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

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

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

C18H23N3S	F(000) = 672
Mr = 313.45	Dx = 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

Bruker SMART APEX diffractometer	3988 independent reflections
Radiation source: sealed tube	2816 reflections with I > 2σ(I)
graphite	Rint = 0.066
φ and ω scans	θmax = 27.9°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −10→9
Tmin = 0.923, Tmax = 0.946	k = −35→35
14278 measured reflections	l = −10→10

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(Fo2) + (0.0443P)2] where P = (Fo2 + 2Fc2)/3
3988 reflections	(Δ/σ)max = 0.001
203 parameters	Δρmax = 0.24 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)