4,4-Bis(4-methyl­phenyl­sulfan­yl)-1,1-diphenyl-2-aza­buta-1,3-diene

Kinghat, R.; Boudiba, H.; Khatyr, A.; Knorr, M.; Kubicki, M.M.

doi:10.1107/S1600536807066615

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o370

doi:10.1107/S1600536807066615

Open

access

4,4-Bis(4-methylphenylsulfanyl)-1,1-diphenyl-2-azabuta-1,3-diene

Rodolphe Kinghat,^a Hamid Boudiba,^a Abderrahim Khatyr,^a Michael Knorr ^a and Marek M. Kubicki ^b ^*

^aInstitut UTINAM UMR CNRS 6213, Université de Franche-Comté, 16 Route de Gray, La Bouloie, 25030 Besançon, France, and ^bInstitute of Molecular Chemistry, Université de Bourgogne, UMR 5260, 9 Avenue A. Savary, 21078 Dijon, France
^*Correspondence e-mail: marek.kubicki@u-bourgogne.fr

(Received 23 October 2007; accepted 12 December 2007; online 4 January 2008)

In the title compound, C₂₉H₂₅NS₂, both the Cl atoms of the azadiene precursor 4,4-dichloro-1,1-diphenyl-2-azabuta-1,3-diene are replaced by two vicinal S-p-tolyl substituents attached to the terminal C atom of a π-conjugated 2-azabutadiene array. The azadiene chain is planar to within 0.01 Å. One of the phenyl rings seems to be slightly π-conjugated with the azadiene core [dihedral angle 5.1 (2)°].

Related literature

Some related structures of alkoxo- (Jacquot et al., 2000 ), cyano- (Jacquot-Rousseau et al., 2002 ) and ⁱPrS-substituted (Jacquot-Rousseau et al., 2005 ) 4,4-dichloro-1,1-diphenyl-2-azabuta-1,3-dienes (Jacquot et al., 1999 ) have been reported. For related literature, see: Tanimoto et al. (1976 ); Truce & Boudakian (1956 ).

Experimental

Crystal data

C₂₉H₂₅NS₂
M_r = 451.66
Triclinic, $[P \overline 1]$
a = 6.9340 (10) Å
b = 12.3009 (2) Å
c = 14.4247 (3) Å
α = 101.7371 (8)°
β = 98.2522 (7)°
γ = 93.0400 (10)°
V = 1187.90 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 120 (2) K
0.2 × 0.12 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
7710 measured reflections
5329 independent reflections
4695 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.089
S = 1.04
5329 reflections
317 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: KappaCCD Server Software (Nonius, 1997 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807066615/gw2031sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807066615/gw2031Isup2.hkl

checkCIF report

Comment top

The investigations of Truce and Boudakian on the reactivity of 1,1-dichloroethylene (1) towards an excess of sodium p-toluenethiolate have shown that this reaction affords exclusively cis-1,2-bis-(p-tolylmercapto) ethane (2). The intermediacy of an alkyne species ArSCCH has been suggested to rationalize this interesting rearrangement reaction which implies some addition–elimination sequences (Truce & Boudakian, 1956). Another research group has later confirmed these findings (Tanimoto et al., 1976) (Fig. 2). In the context of our interest in developing novel π-conjugated dithioether compounds as ligands for coordination chemistry, we have recently reported on the synthesis and crystal structure of [(i-PrS)₂C=C(H)—N=CPh₂] (4a), obtained by reaction of an excess of sodium i-propylthiolate with 4,4-dichloro-1,1-diphenyl-2-azabuta-1,3-diene (3) in DMF as solvent (Jacquot-Rousseau et al., 2005). In the light of the results mentioned above, we were intrigued whether the reaction of (3) (Jacquot et al., 1999) with sodium p-toluenethiolate would lead to [(p-tolylS)₂C=C(H)—N=CPh₂] (4 b) or to an rearranged product bearing the two –S-p-tolyl substituents on two different carbon atoms, similar to the case of olefin (2) (Fig. 3).

The molecular structure of (4 b) is shown in Fig. 1. The transoid conformation of the azabutadiene chain found in precursor (3) and in the S-i-propyl derivative (4a) is also observed in the crystal structure of (4 b). In contrast to compound (2), both the S-p-tolyl substituents are attached to the same C(3) atom.

One may expect that one of the two phenyl groups bound to C(1) makes part of the phenyl/azadiene chain π-conjugation. In fact, a dihedral angle between C10–C15 phenyl plane and that of azadiene chain C1—N—C2—C3 is equal only to 5.1 (2)°. Note that these dihedral angles amount to 28.7 (1)° in precursor (3) and 38.8 (3)° in (4a). An obvious question arises: the reported values of dihedral angles are due to the electronic structures of compounds (3) and (4) or to the packing in the crystals? This problem requires some calculations on the electronic structure of (4 b) and will be separately treated elsewhere.

Related literature top

Some related structures of alkoxo- (Jacquot et al., 2000), cyano- (Jacquot-Rousseau et al., 2002) and i-PrS-substituted (Jacquot-Rousseau et al., 2005) 4,4-dichloro-1,1-diphenyl-2-azabuta-1,3-dienes (Jacquot et al., 1999) have been reported. For related literature, see: Tanimoto et al. (1976); Truce & Boudakian (1956).

Experimental top

4,4-Dichloro-1,1-diphenyl-2-azabuta-1,3-diene (3) (1.1 mmol) was stirred with an excess of 4-toluenethiolate (8 mmol) in dry DMF (10 ml). The reaction mixture was kept at room temperature for 8 h, then poured into water (100 ml) and extracted with diethyl ether (150 ml). The organic solution was washed three times with water, dried over anhydrous sodium sulfate and evaporated. The crude residue was recristallized from ethanol (75% yield). 1H NMR: δ = 2.30 p.p.m. (s, 3H, Ar—CH3); 2.33 p.p.m. (s, 3H, Ar—CH3);), 6.99–7.02 p.p.m. (m, 8H, phenyl) 7.10 p.p.m. (s, 1H, C=CH), 7.23–7.28 p.p.m. (m, 10H, Ar—H).

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

	Fig. 1. View of (4 b) with ellipsoids at the 30% probability level.
	Fig. 2. p-S-tolyl substitution on 1,1-dichloroethylene.
	Fig. 3. p-S-tolyl substitution on an azadienic chain.

4,4-Bis(4-methylphenylsulfanyl)-1,1-diphenyl-2-azabuta-1,3-diene top

Crystal data top

C₂₉H₂₅NS₂	Z = 2
M_r = 451.66	F(000) = 476
Triclinic, P1	D_x = 1.263 Mg m⁻³
Hall symbol: -P 1	Melting point: 382 K
a = 6.934 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.3009 (2) Å	Cell parameters from 3954 reflections
c = 14.4247 (3) Å	θ = 1.0–27.5°
α = 101.7371 (8)°	µ = 0.24 mm⁻¹
β = 98.2522 (7)°	T = 120 K
γ = 93.040 (1)°	Irregular, yellow
V = 1187.90 (4) Å³	0.2 × 0.12 × 0.08 mm

Data collection top

Nonius KappaCCD diffractometer	4695 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
Graphite monochromator	θ_max = 27.4°, θ_min = 1.5°
CCD scans	h = −8→8
7710 measured reflections	k = −12→15
5329 independent reflections	l = −18→18

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)] = 0.034	Hydrogen site location: mixed
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0329P)² + 0.5208P] where P = (F_o² + 2F_c²)/3
5329 reflections	(Δ/σ)_max = 0.001
317 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₂₉H₂₅NS₂	γ = 93.040 (1)°
M_r = 451.66	V = 1187.90 (4) Å³
Triclinic, P1	Z = 2
a = 6.934 (1) Å	Mo Kα radiation
b = 12.3009 (2) Å	µ = 0.24 mm⁻¹
c = 14.4247 (3) Å	T = 120 K
α = 101.7371 (8)°	0.2 × 0.12 × 0.08 mm
β = 98.2522 (7)°

Data collection top

Nonius KappaCCD diffractometer	4695 reflections with I > 2σ(I)
7710 measured reflections	R_int = 0.019
5329 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.27 e Å⁻³
5329 reflections	Δρ_min = −0.25 e Å⁻³
317 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	0.22781 (5)	0.37867 (3)	0.35024 (2)	0.02290 (9)
S2	0.43297 (4)	0.52776 (3)	0.23783 (2)	0.02161 (9)
N	0.48657 (16)	0.21771 (9)	0.26950 (8)	0.0221 (2)
C1	0.58163 (18)	0.13424 (11)	0.23639 (9)	0.0204 (3)
C2	0.50043 (19)	0.31661 (11)	0.23787 (10)	0.0227 (3)
C3	0.39300 (18)	0.40002 (11)	0.27163 (9)	0.0200 (3)
C4	0.71038 (19)	0.13495 (10)	0.16171 (9)	0.0206 (3)
C5	0.6304 (2)	0.12895 (14)	0.06658 (11)	0.0328 (3)
H5	0.4953	0.1238	0.0489	0.039*
C6	0.7506 (3)	0.13066 (16)	−0.00219 (12)	0.0415 (4)
H6	0.6960	0.1270	−0.0656	0.050*
C7	0.9508 (2)	0.13778 (14)	0.02340 (12)	0.0364 (4)
H7	1.0312	0.1378	−0.0230	0.044*
C8	1.0317 (2)	0.14488 (13)	0.11728 (12)	0.0350 (3)
H8	1.1670	0.1506	0.1345	0.042*
C9	0.9128 (2)	0.14354 (12)	0.18644 (11)	0.0287 (3)
H9	0.9686	0.1484	0.2499	0.034*
C10	0.56071 (18)	0.03303 (11)	0.27658 (9)	0.0207 (3)
C11	0.6700 (2)	−0.05758 (11)	0.25308 (10)	0.0250 (3)
H11	0.7553	−0.0568	0.2089	0.030*
C12	0.6528 (2)	−0.14933 (12)	0.29507 (11)	0.0293 (3)
H12	0.7284	−0.2087	0.2799	0.035*
C13	0.5238 (2)	−0.15238 (12)	0.35923 (11)	0.0285 (3)
H13	0.5126	−0.2136	0.3874	0.034*
C14	0.4112 (2)	−0.06400 (13)	0.38151 (12)	0.0322 (3)
H14	0.3228	−0.0664	0.4240	0.039*
C15	0.4296 (2)	0.02781 (12)	0.34092 (11)	0.0290 (3)
H15	0.3537	0.0869	0.3566	0.035*
C16	0.19592 (18)	0.55484 (11)	0.18701 (9)	0.0200 (3)
C17	0.05190 (19)	0.47143 (11)	0.13858 (10)	0.0231 (3)
H17	0.0744	0.3969	0.1344	0.028*
C18	−0.1256 (2)	0.50030 (12)	0.09652 (10)	0.0258 (3)
H18	−0.2222	0.4443	0.0652	0.031*
C19	−0.1623 (2)	0.61123 (12)	0.10010 (10)	0.0249 (3)
C20	−0.0167 (2)	0.69289 (12)	0.14901 (10)	0.0269 (3)
H20	−0.0387	0.7675	0.1528	0.032*
C21	0.1609 (2)	0.66593 (11)	0.19237 (10)	0.0255 (3)
H21	0.2563	0.7221	0.2249	0.031*
C22	−0.3522 (2)	0.64249 (15)	0.05100 (12)	0.0328 (3)
C23	0.16434 (19)	0.51460 (10)	0.39797 (9)	0.0195 (3)
C24	−0.02989 (19)	0.53814 (11)	0.38031 (9)	0.0217 (3)
H24	−0.1223	0.4848	0.3408	0.026*
C25	−0.08547 (19)	0.64104 (11)	0.42158 (10)	0.0233 (3)
H25	−0.2158	0.6559	0.4098	0.028*
C26	0.0502 (2)	0.72288 (11)	0.48054 (9)	0.0222 (3)
C27	0.2438 (2)	0.69758 (11)	0.49862 (9)	0.0231 (3)
H27	0.3362	0.7509	0.5383	0.028*
C28	0.30109 (19)	0.59443 (11)	0.45858 (9)	0.0218 (3)
H28	0.4305	0.5786	0.4721	0.026*
C29	−0.0105 (3)	0.83537 (13)	0.52391 (12)	0.0316 (3)
H2	0.587 (2)	0.3271 (13)	0.1916 (11)	0.023 (4)*
H221	−0.460 (3)	0.6112 (18)	0.0711 (16)	0.060 (6)*
H222	−0.370 (3)	0.6152 (19)	−0.0180 (18)	0.065 (7)*
H223	−0.357 (3)	0.722 (2)	0.0618 (17)	0.075 (7)*
H291	−0.049 (3)	0.8755 (17)	0.4753 (15)	0.050 (5)*
H292	0.094 (3)	0.8815 (18)	0.5682 (15)	0.055 (6)*
H293	−0.120 (3)	0.8270 (19)	0.5548 (16)	0.066 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02781 (18)	0.01708 (16)	0.02706 (18)	0.00498 (12)	0.01078 (13)	0.00695 (13)
S2	0.01964 (16)	0.02080 (17)	0.02704 (18)	0.00391 (12)	0.00537 (12)	0.00951 (13)
N	0.0233 (5)	0.0201 (5)	0.0235 (6)	0.0061 (4)	0.0038 (4)	0.0045 (4)
C1	0.0199 (6)	0.0198 (6)	0.0200 (6)	0.0040 (5)	0.0010 (5)	0.0021 (5)
C2	0.0229 (6)	0.0226 (6)	0.0235 (7)	0.0053 (5)	0.0042 (5)	0.0059 (5)
C3	0.0207 (6)	0.0193 (6)	0.0206 (6)	0.0035 (5)	0.0028 (5)	0.0056 (5)
C4	0.0235 (6)	0.0162 (6)	0.0228 (6)	0.0048 (5)	0.0053 (5)	0.0037 (5)
C5	0.0273 (7)	0.0471 (9)	0.0257 (7)	0.0121 (6)	0.0035 (6)	0.0095 (7)
C6	0.0454 (9)	0.0584 (11)	0.0255 (8)	0.0162 (8)	0.0095 (7)	0.0144 (7)
C7	0.0398 (9)	0.0389 (9)	0.0375 (9)	0.0084 (7)	0.0209 (7)	0.0126 (7)
C8	0.0250 (7)	0.0377 (8)	0.0433 (9)	−0.0011 (6)	0.0105 (6)	0.0080 (7)
C9	0.0258 (7)	0.0311 (7)	0.0268 (7)	−0.0012 (6)	0.0014 (6)	0.0035 (6)
C10	0.0217 (6)	0.0198 (6)	0.0197 (6)	0.0033 (5)	0.0022 (5)	0.0023 (5)
C11	0.0285 (7)	0.0229 (7)	0.0259 (7)	0.0064 (5)	0.0090 (5)	0.0056 (5)
C12	0.0346 (8)	0.0218 (7)	0.0345 (8)	0.0089 (6)	0.0100 (6)	0.0077 (6)
C13	0.0342 (7)	0.0225 (7)	0.0306 (8)	0.0016 (6)	0.0057 (6)	0.0095 (6)
C14	0.0349 (8)	0.0300 (8)	0.0360 (8)	0.0042 (6)	0.0166 (6)	0.0093 (6)
C15	0.0305 (7)	0.0251 (7)	0.0351 (8)	0.0092 (6)	0.0137 (6)	0.0070 (6)
C16	0.0212 (6)	0.0232 (6)	0.0190 (6)	0.0062 (5)	0.0068 (5)	0.0087 (5)
C17	0.0270 (7)	0.0213 (6)	0.0227 (7)	0.0051 (5)	0.0055 (5)	0.0064 (5)
C18	0.0252 (7)	0.0292 (7)	0.0233 (7)	0.0024 (5)	0.0025 (5)	0.0072 (6)
C19	0.0240 (7)	0.0330 (7)	0.0224 (7)	0.0093 (5)	0.0078 (5)	0.0123 (6)
C20	0.0304 (7)	0.0232 (7)	0.0320 (8)	0.0095 (5)	0.0087 (6)	0.0131 (6)
C21	0.0260 (7)	0.0218 (7)	0.0300 (7)	0.0026 (5)	0.0052 (6)	0.0079 (5)
C22	0.0273 (8)	0.0437 (9)	0.0318 (8)	0.0108 (7)	0.0044 (6)	0.0166 (7)
C23	0.0243 (6)	0.0185 (6)	0.0183 (6)	0.0044 (5)	0.0066 (5)	0.0070 (5)
C24	0.0220 (6)	0.0224 (6)	0.0209 (6)	0.0011 (5)	0.0037 (5)	0.0049 (5)
C25	0.0212 (6)	0.0270 (7)	0.0244 (7)	0.0069 (5)	0.0068 (5)	0.0084 (5)
C26	0.0287 (7)	0.0217 (6)	0.0188 (6)	0.0058 (5)	0.0088 (5)	0.0057 (5)
C27	0.0269 (7)	0.0222 (6)	0.0196 (6)	0.0000 (5)	0.0025 (5)	0.0047 (5)
C28	0.0205 (6)	0.0243 (6)	0.0226 (6)	0.0040 (5)	0.0031 (5)	0.0092 (5)
C29	0.0381 (8)	0.0249 (7)	0.0323 (8)	0.0083 (6)	0.0112 (7)	0.0021 (6)

Geometric parameters (Å, º) top

S1—C3	1.7689 (13)	C14—H14	0.9300
S1—C23	1.7776 (13)	C15—H15	0.9300
S2—C3	1.7572 (13)	C16—C21	1.3892 (19)
S2—C16	1.7781 (13)	C16—C17	1.3919 (19)
N—C1	1.2959 (17)	C17—C18	1.3890 (19)
N—C2	1.3869 (17)	C17—H17	0.9300
C1—C10	1.4851 (18)	C18—C19	1.393 (2)
C1—C4	1.4955 (18)	C18—H18	0.9300
C2—C3	1.3515 (18)	C19—C20	1.388 (2)
C2—H2	0.983 (15)	C19—C22	1.5098 (19)
C4—C9	1.3904 (19)	C20—C21	1.3873 (19)
C4—C5	1.3902 (19)	C20—H20	0.9300
C5—C6	1.387 (2)	C21—H21	0.9300
C5—H5	0.9300	C22—H221	0.93 (2)
C6—C7	1.378 (2)	C22—H222	0.97 (2)
C6—H6	0.9300	C22—H223	0.96 (3)
C7—C8	1.373 (2)	C23—C24	1.3912 (18)
C7—H7	0.9300	C23—C28	1.3936 (18)
C8—C9	1.385 (2)	C24—C25	1.3843 (19)
C8—H8	0.9300	C24—H24	0.9300
C9—H9	0.9300	C25—C26	1.3941 (19)
C10—C11	1.3934 (18)	C25—H25	0.9300
C10—C15	1.3974 (19)	C26—C27	1.3942 (19)
C11—C12	1.3927 (19)	C26—C29	1.5062 (19)
C11—H11	0.9300	C27—C28	1.3864 (19)
C12—C13	1.381 (2)	C27—H27	0.9300
C12—H12	0.9300	C28—H28	0.9300
C13—C14	1.384 (2)	C29—H291	0.95 (2)
C13—H13	0.9300	C29—H292	0.97 (2)
C14—C15	1.382 (2)	C29—H293	0.95 (2)

C3—S1—C23	104.31 (6)	C21—C16—C17	119.68 (12)
C3—S2—C16	103.68 (6)	C21—C16—S2	116.76 (10)
C1—N—C2	121.26 (12)	C17—C16—S2	123.46 (10)
N—C1—C10	117.10 (12)	C18—C17—C16	119.57 (12)
N—C1—C4	123.91 (12)	C18—C17—H17	120.2
C10—C1—C4	118.98 (11)	C16—C17—H17	120.2
C3—C2—N	119.27 (12)	C17—C18—C19	121.53 (13)
C3—C2—H2	119.6 (9)	C17—C18—H18	119.2
N—C2—H2	121.2 (9)	C19—C18—H18	119.2
C2—C3—S2	117.32 (10)	C20—C19—C18	117.82 (12)
C2—C3—S1	119.54 (10)	C20—C19—C22	120.64 (13)
S2—C3—S1	123.10 (8)	C18—C19—C22	121.53 (14)
C9—C4—C5	118.69 (13)	C21—C20—C19	121.59 (13)
C9—C4—C1	120.58 (12)	C21—C20—H20	119.2
C5—C4—C1	120.73 (12)	C19—C20—H20	119.2
C6—C5—C4	120.46 (14)	C20—C21—C16	119.80 (13)
C6—C5—H5	119.8	C20—C21—H21	120.1
C4—C5—H5	119.8	C16—C21—H21	120.1
C7—C6—C5	120.06 (15)	C19—C22—H221	111.6 (13)
C7—C6—H6	120.0	C19—C22—H222	111.9 (13)
C5—C6—H6	120.0	H221—C22—H222	105.5 (18)
C8—C7—C6	120.05 (14)	C19—C22—H223	111.4 (14)
C8—C7—H7	120.0	H221—C22—H223	109.5 (19)
C6—C7—H7	120.0	H222—C22—H223	106.6 (19)
C7—C8—C9	120.25 (14)	C24—C23—C28	119.57 (12)
C7—C8—H8	119.9	C24—C23—S1	118.78 (10)
C9—C8—H8	119.9	C28—C23—S1	121.44 (10)
C8—C9—C4	120.48 (14)	C25—C24—C23	119.96 (12)
C8—C9—H9	119.8	C25—C24—H24	120.0
C4—C9—H9	119.8	C23—C24—H24	120.0
C11—C10—C15	118.28 (12)	C24—C25—C26	121.25 (12)
C11—C10—C1	122.05 (12)	C24—C25—H25	119.4
C15—C10—C1	119.66 (12)	C26—C25—H25	119.4
C12—C11—C10	120.62 (13)	C27—C26—C25	118.15 (12)
C12—C11—H11	119.7	C27—C26—C29	120.85 (13)
C10—C11—H11	119.7	C25—C26—C29	121.01 (13)
C13—C12—C11	120.18 (13)	C28—C27—C26	121.20 (12)
C13—C12—H12	119.9	C28—C27—H27	119.4
C11—C12—H12	119.9	C26—C27—H27	119.4
C12—C13—C14	119.75 (13)	C27—C28—C23	119.84 (12)
C12—C13—H13	120.1	C27—C28—H28	120.1
C14—C13—H13	120.1	C23—C28—H28	120.1
C15—C14—C13	120.26 (14)	C26—C29—H291	110.6 (12)
C15—C14—H14	119.9	C26—C29—H292	112.6 (13)
C13—C14—H14	119.9	H291—C29—H292	106.3 (17)
C14—C15—C10	120.89 (13)	C26—C29—H293	110.2 (14)
C14—C15—H15	119.6	H291—C29—H293	106.8 (18)
C10—C15—H15	119.6	H292—C29—H293	110.1 (18)

Experimental details

Crystal data
Chemical formula	C₂₉H₂₅NS₂
M_r	451.66
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	6.934 (1), 12.3009 (2), 14.4247 (3)
α, β, γ (°)	101.7371 (8), 98.2522 (7), 93.040 (1)
V (Å³)	1187.90 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.2 × 0.12 × 0.08

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7710, 5329, 4695
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.089, 1.04
No. of reflections	5329
No. of parameters	317
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.25

Computer programs: KappaCCD Server Software (Nonius, 1997), SCALEPACK (Otwinowski & Minor, 1997), DENZO (Otwinowski & Minor, 1997) and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997).

Acknowledgements

CNRS is acknowledged for financial support

References

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Jacquot, S., Belaissaoui, A., Schmitt, G., Laude, B., Kubicki, M. M. & Blacque, O. (1999). Eur. J. Org. Chem. pp. 1541–1544. CrossRef Google Scholar
Jacquot, S., Schmitt, G., Laude, B., Kubicki, M. M. & Blacque, O. (2000). Eur. J. Org. Chem. pp. 1235–1239. CrossRef Google Scholar
Jacquot-Rousseau, S., Khatyr, A., Schmitt, G., Knorr, M., Kubicki, M. M. & Blacque, O. (2005). Inorg. Chem. Commun. 8, 610–613. Web of Science CSD CrossRef CAS Google Scholar
Jacquot-Rousseau, S., Schmitt, G., Laude, B., Kubicki, M. M. & Blacque, O. (2002). J. Chem. Res. (S), pp. 151–152. Google Scholar
Nonius (1997). KappaCCD Server Software. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Tanimoto, S., Taniyasu, R., Takahashi, T., Miyake, T. & Okano, M. (1976). Bull. Chem. Soc. Jpn, 49, 1931–1936. CrossRef CAS Web of Science Google Scholar
Truce, W. E. & Boudakian, M. M. (1956). J. Am. Chem. Soc. 78, 2748–2751. CrossRef CAS Web of Science Google Scholar