Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807017680/om2119sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807017680/om2119Isup2.hkl |
CCDC reference: 647598
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (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
For related literature, see: Allen et al. (1987); Arul Murugan (2005); Whitesell (1989); Yasuda et al. (2003).
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).
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).
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).
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.
C18H18S2 | Dx = 1.275 Mg m−3 |
Mr = 298.44 | Melting point: 321 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 2284 reflections |
a = 8.2205 (2) Å | θ = 3.3–25.3° |
b = 10.1243 (3) Å | µ = 0.33 mm−1 |
c = 18.6848 (7) Å | T = 295 K |
V = 1555.08 (8) Å3 | Prism, colourless |
Z = 4 | 0.20 × 0.15 × 0.10 mm |
F(000) = 632 |
Bruker APEXII diffractometer | 1481 independent reflections |
Radiation source: fine-focus sealed tube | 1154 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ω and φ scans | θmax = 25.8°, θmin = 3.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −10→9 |
Tmin = 0.935, Tmax = 0.969 | k = −12→12 |
7493 measured reflections | l = −22→18 |
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)] = 0.039 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.102 | Only 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 parameters | Δρmax = 0.27 e Å−3 |
4 restraints | Δρmin = −0.28 e Å−3 |
C18H18S2 | V = 1555.08 (8) Å3 |
Mr = 298.44 | Z = 4 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 8.2205 (2) Å | µ = 0.33 mm−1 |
b = 10.1243 (3) Å | T = 295 K |
c = 18.6848 (7) Å | 0.20 × 0.15 × 0.10 mm |
Bruker APEXII diffractometer | 1481 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 1154 reflections with I > 2σ(I) |
Tmin = 0.935, Tmax = 0.969 | Rint = 0.031 |
7493 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 4 restraints |
wR(F2) = 0.102 | Only H-atom coordinates refined |
S = 1.05 | Δρmax = 0.27 e Å−3 |
1481 reflections | Δρmin = −0.28 e Å−3 |
125 parameters |
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 | Occ. (<1) | |
S1 | 0.67527 (7) | 0.55095 (6) | 0.06937 (4) | 0.0543 (3) | |
C1 | 0.5499 (2) | 0.4583 (2) | 0.12679 (13) | 0.0396 (5) | |
C2 | 0.4799 (3) | 0.5278 (3) | 0.18288 (14) | 0.0506 (6) | |
H2 | 0.502 (3) | 0.619 (3) | 0.1868 (14) | 0.061* | |
C3 | 0.3811 (3) | 0.4647 (3) | 0.23169 (15) | 0.0591 (7) | |
H3 | 0.337 (3) | 0.514 (3) | 0.2689 (16) | 0.071* | |
C4 | 0.3508 (3) | 0.3319 (3) | 0.22554 (15) | 0.0595 (7) | |
H4 | 0.281 (4) | 0.292 (3) | 0.2591 (16) | 0.071* | |
C5 | 0.4192 (3) | 0.2630 (3) | 0.16993 (16) | 0.0561 (7) | |
H5 | 0.402 (4) | 0.175 (3) | 0.1642 (15) | 0.067* | |
C6 | 0.5177 (3) | 0.3248 (2) | 0.12034 (15) | 0.0465 (6) | |
H6 | 0.558 (3) | 0.280 (3) | 0.0834 (15) | 0.056* | |
C7 | 0.7789 (3) | 0.4342 (3) | 0.0123 (2) | 0.0632 (8) | |
H7A | 0.717 (4) | 0.407 (3) | −0.0221 (17) | 0.076* | |
H7B | 0.802 (4) | 0.358 (3) | 0.0441 (16) | 0.076* | |
C8 | 0.9245 (3) | 0.5055 (3) | −0.02066 (15) | 0.0408 (8) | 0.789 (5) |
C9 | 0.9157 (4) | 0.5764 (4) | −0.07846 (18) | 0.0758 (10) | |
H9A | 0.993 (4) | 0.625 (3) | −0.1050 (19) | 0.091* | |
H9B | 0.823 (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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0416 (4) | 0.0445 (4) | 0.0769 (5) | −0.0037 (3) | 0.0195 (3) | −0.0058 (3) |
C1 | 0.0257 (10) | 0.0446 (12) | 0.0484 (13) | 0.0013 (9) | −0.0041 (9) | −0.0025 (10) |
C2 | 0.0424 (13) | 0.0500 (14) | 0.0594 (16) | 0.0016 (11) | −0.0009 (12) | −0.0115 (12) |
C3 | 0.0494 (15) | 0.078 (2) | 0.0497 (16) | 0.0101 (14) | 0.0057 (12) | −0.0054 (14) |
C4 | 0.0488 (16) | 0.0727 (19) | 0.0570 (17) | 0.0017 (13) | 0.0050 (13) | 0.0182 (15) |
C5 | 0.0506 (15) | 0.0475 (14) | 0.0702 (19) | −0.0015 (12) | −0.0018 (13) | 0.0106 (14) |
C6 | 0.0402 (13) | 0.0432 (13) | 0.0560 (15) | 0.0036 (10) | 0.0015 (11) | −0.0029 (12) |
C7 | 0.0370 (14) | 0.0690 (18) | 0.084 (2) | −0.0144 (12) | 0.0162 (13) | −0.0314 (16) |
C8 | 0.0322 (14) | 0.0499 (16) | 0.0401 (18) | 0.0041 (12) | −0.0037 (12) | −0.0032 (14) |
C9 | 0.0459 (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) |
S1—C1 | 1.759 (2) | C7—C8 | 1.527 (4) |
S1—C7 | 1.806 (3) | C7—C8' | 1.593 (5) |
C1—C6 | 1.382 (3) | C7—H7A | 0.86 (3) |
C1—C2 | 1.387 (3) | C7—H7B | 1.00 (3) |
C2—C3 | 1.378 (4) | C8—C8'i | 0.984 (5) |
C2—H2 | 0.94 (3) | C8—C8' | 1.097 (5) |
C3—C4 | 1.373 (4) | C8—C9 | 1.299 (4) |
C3—H3 | 0.93 (3) | C8—C8i | 1.467 (5) |
C4—C5 | 1.372 (4) | C9—C8'i | 1.387 (4) |
C4—H4 | 0.94 (3) | C9—H9A | 0.94 (4) |
C5—C6 | 1.381 (4) | C9—H9B | 0.86 (4) |
C5—H5 | 0.91 (3) | C8'—C9i | 1.387 (4) |
C6—H6 | 0.89 (3) | C8'—C8'i | 1.480 (6) |
C1—S1—C7 | 106.72 (13) | C8'—C7—S1 | 106.5 (4) |
C6—C1—C2 | 118.8 (2) | C8—C7—H7A | 108 (2) |
C6—C1—S1 | 125.47 (19) | C8'—C7—H7A | 138 (2) |
C2—C1—S1 | 115.70 (18) | S1—C7—H7A | 111 (2) |
C3—C2—C1 | 120.6 (2) | C8—C7—H7B | 117.4 (18) |
C3—C2—H2 | 120.9 (16) | C8'—C7—H7B | 78.7 (18) |
C1—C2—H2 | 118.5 (17) | S1—C7—H7B | 104.4 (18) |
C4—C3—C2 | 120.4 (3) | H7A—C7—H7B | 108 (3) |
C4—C3—H3 | 121.1 (19) | C9—C8—C8i | 121.8 (4) |
C2—C3—H3 | 118.6 (19) | C9—C8—C7 | 123.6 (3) |
C5—C4—C3 | 119.2 (3) | C8i—C8—C7 | 114.6 (3) |
C5—C4—H4 | 122.2 (18) | C8—C9—H9A | 133 (2) |
C3—C4—H4 | 118.6 (17) | C8'i—C9—H9A | 91 (2) |
C4—C5—C6 | 121.2 (3) | C8—C9—H9B | 116 (2) |
C4—C5—H5 | 121.6 (19) | C8'i—C9—H9B | 159 (2) |
C6—C5—H5 | 117.2 (19) | H9A—C9—H9B | 111 (3) |
C5—C6—C1 | 119.8 (2) | C9i—C8'—C8'i | 111.6 (5) |
C5—C6—H6 | 120.2 (17) | C9i—C8'—C7 | 139.9 (3) |
C1—C6—H6 | 120.0 (17) | C8'i—C8'—C7 | 107.7 (4) |
C8—C7—S1 | 107.37 (19) | ||
C7—S1—C1—C6 | −10.0 (3) | S1—C1—C6—C5 | 178.79 (19) |
C7—S1—C1—C2 | 169.71 (19) | C1—S1—C7—C8 | −162.4 (2) |
C6—C1—C2—C3 | 0.5 (4) | C1—S1—C7—C8' | −119.4 (2) |
S1—C1—C2—C3 | −179.2 (2) | S1—C7—C8—C9 | −85.5 (4) |
C1—C2—C3—C4 | 0.1 (4) | S1—C7—C8—C8i | 90.9 (4) |
C2—C3—C4—C5 | −0.4 (4) | S1—C7—C8'—C9i | 74.6 (12) |
C3—C4—C5—C6 | 0.1 (4) | S1—C7—C8'—C8'i | −93.6 (10) |
C4—C5—C6—C1 | 0.6 (4) | C7—C8—C8i—C7i | 180.0 (3) |
C2—C1—C6—C5 | −0.9 (4) | C7—C8'—C8'i—C7i | 180.0 (3) |
Symmetry code: (i) −x+2, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9B···Cg1ii | 0.89 (3) | 2.67 (3) | 3.528 (3) | 173 (3) |
Symmetry code: (ii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C18H18S2 |
Mr | 298.44 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 295 |
a, b, c (Å) | 8.2205 (2), 10.1243 (3), 18.6848 (7) |
V (Å3) | 1555.08 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.33 |
Crystal size (mm) | 0.20 × 0.15 × 0.10 |
Data collection | |
Diffractometer | Bruker APEXII |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.935, 0.969 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7493, 1481, 1154 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.611 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.102, 1.05 |
No. of reflections | 1481 |
No. of parameters | 125 |
No. of restraints | 4 |
H-atom treatment | Only H-atom coordinates refined |
Δρmax, Δρmin (e Å−3) | 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.
S1—C1 | 1.759 (2) | C8—C9 | 1.299 (4) |
S1—C7 | 1.806 (3) | C8—C8i | 1.467 (5) |
C7—C8 | 1.527 (4) | C8'—C9i | 1.387 (4) |
C7—C8' | 1.593 (5) | C8'—C8'i | 1.480 (6) |
C1—S1—C7 | 106.72 (13) | C9—C8—C7 | 123.6 (3) |
C6—C1—S1 | 125.47 (19) | C8i—C8—C7 | 114.6 (3) |
C2—C1—S1 | 115.70 (18) | C9i—C8'—C8'i | 111.6 (5) |
C8—C7—S1 | 107.37 (19) | C9i—C8'—C7 | 139.9 (3) |
C8'—C7—S1 | 106.5 (4) | C8'i—C8'—C7 | 107.7 (4) |
C9—C8—C8i | 121.8 (4) | ||
C7—S1—C1—C6 | −10.0 (3) | S1—C7—C8'—C9i | 74.6 (12) |
C1—S1—C7—C8 | −162.4 (2) | S1—C7—C8'—C8'i | −93.6 (10) |
C1—S1—C7—C8' | −119.4 (2) | C7—C8—C8i—C7i | 180.0 (3) |
S1—C7—C8—C9 | −85.5 (4) | C7—C8'—C8'i—C7i | 180.0 (3) |
S1—C7—C8—C8i | 90.9 (4) |
Symmetry code: (i) −x+2, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9B···Cg1ii | 0.89 (3) | 2.67 (3) | 3.528 (3) | 173 (3) |
Symmetry code: (ii) −x+1, −y+1, −z. |
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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.