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In the title compound, C18H18S2, the planar divinyl group displays a static flip-flop disorder. The mol­ecule has crystallographically imposed C2 symmetry. The site occupancies of the major and minor components of the disordered divinyl plane are 0.789 (5) and 0.212 (6), respectively. Co-operative C—H...π inter­actions form mol­ecular dimers. The dimers associate in a one-dimensional chain along the a axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807017680/om2119sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807017680/om2119Isup2.hkl
Contains datablock I

CCDC reference: 647598

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.004 Å
  • Disorder in main residue
  • R factor = 0.039
  • wR factor = 0.102
  • Data-to-parameter ratio = 11.8

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C7 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C8 PLAT301_ALERT_3_C Main Residue Disorder ......................... 9.00 Perc. PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.21 Ratio
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The title compound, ({2-methylidene-3-[(phenylsulfanyl)methyl]but-3-en-1-yl}sulfanyl)benzene, (I), is synthesized as a chiral molecule possessing C2 symmetry. The introduction of C2 symmetry in a chiral ligand is a useful strategy of stereochemically restricting the number of diastereomeric transition states (Whitesell, 1989).

Selected bond distances and bond angles are provided in Table 1. Due to the molecular symmetry (C2), which is retained in the crystal, the asymmetric unit is composed of one-half of the molecule (Z' = 1/2). In the crystal structure, the flip of the central planar divinyl (2,3-dimethyl-1,3-butadiene) group about the C7—C7(i) axis (symmetry code (i): -x + 2, -y + 1, -z) gives rise to a static configurational disorder. As a result of that, the divinyl plane is disordered over two sites with site occupancies of 0.789 (5) and 0.212 (6). Because of the molecular and crystal symmetry, only the intermediate C-atoms of the divinyl occupies two distinct sites (C8/C8'). The flip-flop disorder of divinyl plane, illustrated in Fig. 1, is similar to classical peptide plane flip and also previously observed in 4-vinyl benzoic acid (Yasuda et al., 2003; Arul Murugan, 2005).

The least-square planes in (I) are defined by thiophenyl (S1/C1—C6) and disordered divinyl groups (atoms: C7/C8/C9,C7(i)/C8(i)/C9(i); symmetry code (i): -x + 2, -y + 1, -z) [C7/C8'/C9/C7(i)/C8'(i)/C9(i)]. The data inside the square bracket correspond to the minor component of the disordered divinyl group. The inclination angle between these two planes is 87.5 (1)[87.9 (1)]° and the maximum out of plane deviations are 0.01 (1)Å for atom S1, and, -0.02 (1)[-0.05 (1)]Å, for atom C8[C8'], respectively. Essential torsion angles are given in Table 1.

Crystal packing is purely governed by weak intermolecular forces. The cooperative C9—H9B ··· Cg1(ii) interaction (symmetry code (ii): 1 - x, 1 - y, -z) form a closed dimers (Table 2). These dimers are linked again by the same C—H ··· π interactions and form a one-dimensional chain along a axis. Packing view, in Fig. 2, highlight cooperative intermolecular association.

Related literature top

For related literature, see: Allen et al. (1987); Arul Murugan (2005); Whitesell (1989); Yasuda et al. (2003).

Experimental top

2,3 - bis(iodomethyl)buta-1,3-diene (1 mol) was dropwise added to sodium thiophenoxide (2 mol) with cooling. The reaction mixture was stirred overnight at room temperature and poured on crushed ice. The resulting solids were filtered and dissolved in ether. The ether extract was washed with sodium thiosulfate and 10% sodium hydroxide and finally with water. The product was obtained by removal of ether after drying, which was recrystallized from hexane at room temperature (yield, 58%; m.p. 321 K).

Refinement top

The bond distances (Allen et al., 1987) of minor component of the disordered divinyl group was restrained to C7—C8' = 1.593 (5); C8'—C8'(i) = 1.480 (6); C8'—C9(i) = 1.387 (4) Å; symmetry code (i): -x + 2, -y + 1, -z. The same anisotropic displacement parameters were assigned to both the disordered atoms C8 and C8'. The positions of all H atoms were freely refined. The distances with H-atoms are in ranges:- Car—H = 0.89 (3)–0.94 (3); Csp2—H = 0.86 (4)–0.94 (4); and Cmethylene—H = 0.86 (3) - 1.00 (3)%A with Uiso(H) = 1.2 Ueq(C).

Structure description top

The title compound, ({2-methylidene-3-[(phenylsulfanyl)methyl]but-3-en-1-yl}sulfanyl)benzene, (I), is synthesized as a chiral molecule possessing C2 symmetry. The introduction of C2 symmetry in a chiral ligand is a useful strategy of stereochemically restricting the number of diastereomeric transition states (Whitesell, 1989).

Selected bond distances and bond angles are provided in Table 1. Due to the molecular symmetry (C2), which is retained in the crystal, the asymmetric unit is composed of one-half of the molecule (Z' = 1/2). In the crystal structure, the flip of the central planar divinyl (2,3-dimethyl-1,3-butadiene) group about the C7—C7(i) axis (symmetry code (i): -x + 2, -y + 1, -z) gives rise to a static configurational disorder. As a result of that, the divinyl plane is disordered over two sites with site occupancies of 0.789 (5) and 0.212 (6). Because of the molecular and crystal symmetry, only the intermediate C-atoms of the divinyl occupies two distinct sites (C8/C8'). The flip-flop disorder of divinyl plane, illustrated in Fig. 1, is similar to classical peptide plane flip and also previously observed in 4-vinyl benzoic acid (Yasuda et al., 2003; Arul Murugan, 2005).

The least-square planes in (I) are defined by thiophenyl (S1/C1—C6) and disordered divinyl groups (atoms: C7/C8/C9,C7(i)/C8(i)/C9(i); symmetry code (i): -x + 2, -y + 1, -z) [C7/C8'/C9/C7(i)/C8'(i)/C9(i)]. The data inside the square bracket correspond to the minor component of the disordered divinyl group. The inclination angle between these two planes is 87.5 (1)[87.9 (1)]° and the maximum out of plane deviations are 0.01 (1)Å for atom S1, and, -0.02 (1)[-0.05 (1)]Å, for atom C8[C8'], respectively. Essential torsion angles are given in Table 1.

Crystal packing is purely governed by weak intermolecular forces. The cooperative C9—H9B ··· Cg1(ii) interaction (symmetry code (ii): 1 - x, 1 - y, -z) form a closed dimers (Table 2). These dimers are linked again by the same C—H ··· π interactions and form a one-dimensional chain along a axis. Packing view, in Fig. 2, highlight cooperative intermolecular association.

For related literature, see: Allen et al. (1987); Arul Murugan (2005); Whitesell (1989); Yasuda et al. (2003).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PLATON.

Figures top
[Figure 1] Fig. 1. A Complete view of (I). The planar divinyl group displays a static flip-flop disorder. For clarity, the minor component of the disordered divinyl group are shown with dashed lines. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level. Symmetry code (i): -x + 2, -y + 1, -z.
[Figure 2] Fig. 2. Projection of the crystal packing down the b axis showing cooperative C—H···π interactions forming one-dimensional chain of molecular dimers along a axis. Cg1 is the centroid of (C1—C6) ring. For clarity only the major component of the disorder is shown. Symmetry code (ii): = 1 - x, 1 - y, -z. Color Key: C blue, H white, S green.
{2-Methylidene-3-[(phenylsulfanyl)methyl]but-3-en-1-ylsulfanyl}benzene top
Crystal data top
C18H18S2Dx = 1.275 Mg m3
Mr = 298.44Melting point: 321 K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2284 reflections
a = 8.2205 (2) Åθ = 3.3–25.3°
b = 10.1243 (3) ŵ = 0.33 mm1
c = 18.6848 (7) ÅT = 295 K
V = 1555.08 (8) Å3Prism, colourless
Z = 40.20 × 0.15 × 0.10 mm
F(000) = 632
Data collection top
Bruker APEXII
diffractometer
1481 independent reflections
Radiation source: fine-focus sealed tube1154 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ω and φ scansθmax = 25.8°, θmin = 3.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 109
Tmin = 0.935, Tmax = 0.969k = 1212
7493 measured reflectionsl = 2218
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: difference Fourier map
wR(F2) = 0.102Only H-atom coordinates refined
S = 1.05 w = 1/[σ2(Fo2) + (0.0431P)2 + 0.7833P]
where P = (Fo2 + 2Fc2)/3
1481 reflections(Δ/σ)max = 0.004
125 parametersΔρmax = 0.27 e Å3
4 restraintsΔρmin = 0.28 e Å3
Crystal data top
C18H18S2V = 1555.08 (8) Å3
Mr = 298.44Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 8.2205 (2) ŵ = 0.33 mm1
b = 10.1243 (3) ÅT = 295 K
c = 18.6848 (7) Å0.20 × 0.15 × 0.10 mm
Data collection top
Bruker APEXII
diffractometer
1481 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
1154 reflections with I > 2σ(I)
Tmin = 0.935, Tmax = 0.969Rint = 0.031
7493 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0394 restraints
wR(F2) = 0.102Only H-atom coordinates refined
S = 1.05Δρmax = 0.27 e Å3
1481 reflectionsΔρmin = 0.28 e Å3
125 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
xyzUiso*/UeqOcc. (<1)
S10.67527 (7)0.55095 (6)0.06937 (4)0.0543 (3)
C10.5499 (2)0.4583 (2)0.12679 (13)0.0396 (5)
C20.4799 (3)0.5278 (3)0.18288 (14)0.0506 (6)
H20.502 (3)0.619 (3)0.1868 (14)0.061*
C30.3811 (3)0.4647 (3)0.23169 (15)0.0591 (7)
H30.337 (3)0.514 (3)0.2689 (16)0.071*
C40.3508 (3)0.3319 (3)0.22554 (15)0.0595 (7)
H40.281 (4)0.292 (3)0.2591 (16)0.071*
C50.4192 (3)0.2630 (3)0.16993 (16)0.0561 (7)
H50.402 (4)0.175 (3)0.1642 (15)0.067*
C60.5177 (3)0.3248 (2)0.12034 (15)0.0465 (6)
H60.558 (3)0.280 (3)0.0834 (15)0.056*
C70.7789 (3)0.4342 (3)0.0123 (2)0.0632 (8)
H7A0.717 (4)0.407 (3)0.0221 (17)0.076*
H7B0.802 (4)0.358 (3)0.0441 (16)0.076*
C80.9245 (3)0.5055 (3)0.02066 (15)0.0408 (8)0.789 (5)
C90.9157 (4)0.5764 (4)0.07846 (18)0.0758 (10)
H9A0.993 (4)0.625 (3)0.1050 (19)0.091*
H9B0.823 (4)0.577 (3)0.100 (2)0.091*
C8'0.9684 (6)0.4528 (8)0.0268 (4)0.0408 (18)0.212 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0416 (4)0.0445 (4)0.0769 (5)0.0037 (3)0.0195 (3)0.0058 (3)
C10.0257 (10)0.0446 (12)0.0484 (13)0.0013 (9)0.0041 (9)0.0025 (10)
C20.0424 (13)0.0500 (14)0.0594 (16)0.0016 (11)0.0009 (12)0.0115 (12)
C30.0494 (15)0.078 (2)0.0497 (16)0.0101 (14)0.0057 (12)0.0054 (14)
C40.0488 (16)0.0727 (19)0.0570 (17)0.0017 (13)0.0050 (13)0.0182 (15)
C50.0506 (15)0.0475 (14)0.0702 (19)0.0015 (12)0.0018 (13)0.0106 (14)
C60.0402 (13)0.0432 (13)0.0560 (15)0.0036 (10)0.0015 (11)0.0029 (12)
C70.0370 (14)0.0690 (18)0.084 (2)0.0144 (12)0.0162 (13)0.0314 (16)
C80.0322 (14)0.0499 (16)0.0401 (18)0.0041 (12)0.0037 (12)0.0032 (14)
C90.0459 (17)0.116 (3)0.066 (2)0.0061 (17)0.0062 (14)0.0309 (19)
C8'0.032 (5)0.0499 (14)0.0401 (16)0.0041 (12)0.0037 (14)0.0032 (18)
Geometric parameters (Å, º) top
S1—C11.759 (2)C7—C81.527 (4)
S1—C71.806 (3)C7—C8'1.593 (5)
C1—C61.382 (3)C7—H7A0.86 (3)
C1—C21.387 (3)C7—H7B1.00 (3)
C2—C31.378 (4)C8—C8'i0.984 (5)
C2—H20.94 (3)C8—C8'1.097 (5)
C3—C41.373 (4)C8—C91.299 (4)
C3—H30.93 (3)C8—C8i1.467 (5)
C4—C51.372 (4)C9—C8'i1.387 (4)
C4—H40.94 (3)C9—H9A0.94 (4)
C5—C61.381 (4)C9—H9B0.86 (4)
C5—H50.91 (3)C8'—C9i1.387 (4)
C6—H60.89 (3)C8'—C8'i1.480 (6)
C1—S1—C7106.72 (13)C8'—C7—S1106.5 (4)
C6—C1—C2118.8 (2)C8—C7—H7A108 (2)
C6—C1—S1125.47 (19)C8'—C7—H7A138 (2)
C2—C1—S1115.70 (18)S1—C7—H7A111 (2)
C3—C2—C1120.6 (2)C8—C7—H7B117.4 (18)
C3—C2—H2120.9 (16)C8'—C7—H7B78.7 (18)
C1—C2—H2118.5 (17)S1—C7—H7B104.4 (18)
C4—C3—C2120.4 (3)H7A—C7—H7B108 (3)
C4—C3—H3121.1 (19)C9—C8—C8i121.8 (4)
C2—C3—H3118.6 (19)C9—C8—C7123.6 (3)
C5—C4—C3119.2 (3)C8i—C8—C7114.6 (3)
C5—C4—H4122.2 (18)C8—C9—H9A133 (2)
C3—C4—H4118.6 (17)C8'i—C9—H9A91 (2)
C4—C5—C6121.2 (3)C8—C9—H9B116 (2)
C4—C5—H5121.6 (19)C8'i—C9—H9B159 (2)
C6—C5—H5117.2 (19)H9A—C9—H9B111 (3)
C5—C6—C1119.8 (2)C9i—C8'—C8'i111.6 (5)
C5—C6—H6120.2 (17)C9i—C8'—C7139.9 (3)
C1—C6—H6120.0 (17)C8'i—C8'—C7107.7 (4)
C8—C7—S1107.37 (19)
C7—S1—C1—C610.0 (3)S1—C1—C6—C5178.79 (19)
C7—S1—C1—C2169.71 (19)C1—S1—C7—C8162.4 (2)
C6—C1—C2—C30.5 (4)C1—S1—C7—C8'119.4 (2)
S1—C1—C2—C3179.2 (2)S1—C7—C8—C985.5 (4)
C1—C2—C3—C40.1 (4)S1—C7—C8—C8i90.9 (4)
C2—C3—C4—C50.4 (4)S1—C7—C8'—C9i74.6 (12)
C3—C4—C5—C60.1 (4)S1—C7—C8'—C8'i93.6 (10)
C4—C5—C6—C10.6 (4)C7—C8—C8i—C7i180.0 (3)
C2—C1—C6—C50.9 (4)C7—C8'—C8'i—C7i180.0 (3)
Symmetry code: (i) x+2, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9B···Cg1ii0.89 (3)2.67 (3)3.528 (3)173 (3)
Symmetry code: (ii) x+1, y+1, z.

Experimental details

Crystal data
Chemical formulaC18H18S2
Mr298.44
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)295
a, b, c (Å)8.2205 (2), 10.1243 (3), 18.6848 (7)
V3)1555.08 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.33
Crystal size (mm)0.20 × 0.15 × 0.10
Data collection
DiffractometerBruker APEXII
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.935, 0.969
No. of measured, independent and
observed [I > 2σ(I)] reflections
7493, 1481, 1154
Rint0.031
(sin θ/λ)max1)0.611
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.102, 1.05
No. of reflections1481
No. of parameters125
No. of restraints4
H-atom treatmentOnly H-atom coordinates refined
Δρmax, Δρmin (e Å3)0.27, 0.28

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003), SHELXL97 and PLATON.

Selected geometric parameters (Å, º) top
S1—C11.759 (2)C8—C91.299 (4)
S1—C71.806 (3)C8—C8i1.467 (5)
C7—C81.527 (4)C8'—C9i1.387 (4)
C7—C8'1.593 (5)C8'—C8'i1.480 (6)
C1—S1—C7106.72 (13)C9—C8—C7123.6 (3)
C6—C1—S1125.47 (19)C8i—C8—C7114.6 (3)
C2—C1—S1115.70 (18)C9i—C8'—C8'i111.6 (5)
C8—C7—S1107.37 (19)C9i—C8'—C7139.9 (3)
C8'—C7—S1106.5 (4)C8'i—C8'—C7107.7 (4)
C9—C8—C8i121.8 (4)
C7—S1—C1—C610.0 (3)S1—C7—C8'—C9i74.6 (12)
C1—S1—C7—C8162.4 (2)S1—C7—C8'—C8'i93.6 (10)
C1—S1—C7—C8'119.4 (2)C7—C8—C8i—C7i180.0 (3)
S1—C7—C8—C985.5 (4)C7—C8'—C8'i—C7i180.0 (3)
S1—C7—C8—C8i90.9 (4)
Symmetry code: (i) x+2, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9B···Cg1ii0.89 (3)2.67 (3)3.528 (3)173 (3)
Symmetry code: (ii) x+1, y+1, z.
 

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