 | Acta Crystallographica Section E Acta Crystallographica Section E CRYSTALLOGRAPHIC COMMUNICATIONS |
journal menu
organic compounds
| CRYSTALLOGRAPHIC COMMUNICATIONS |
access1,4-Bis(methylsulfanyl)naphthalene
aDepartment of Physics, Faculty of Arts and Sciences, Cumhuriyet University, 06532 Sivas, Turkey, bDepartment of Physics, Faculty of Arts and Sciences, Erciyes University, 38039 Kayseri, Turkey, cDepartment of Chemistry, Faculty of Arts and Sciences, Gaziosmanpaşa University, 60240 Tokat, Turkey, and dDepartamento Química Física y Analítica, Facultad de Química, Universidad Oviedo, C/ Julián Clavería, 8, 33006 Oviedo (Asturias), Spain
*Correspondence e-mail: akkurt@erciyes.edu.tr
The molecule of the title compound, C12H12S2, is close to planar, with the methyl C atoms deviating by 0.019 (1) and 0.221 (2) Å from the naphthalene mean plane. In the the shortest S⋯S contact of 3.6864 (9) Å is longer than the van der Waals contact distance.
Related literature
For general background, see: Underhill (1992![[Underhill, A. E. (1992). J. Mater. Chem. 2, 1-11.]](../../../../../../logos/arrows/e_arr.gif "Underhill, A. E. (1992). J. Mater. Chem. 2, 1-11.")
); Öncü et al. (2006). For related structures, see: Noreland et al. (1992, 1993). For bond-length data, see: Allen et al. (1987). For van der Waals radii, see: Bondi (1964).
![[Scheme 1]](hb2962scheme1.gif)
Experimental
Crystal data
|
Data collection: XSCANS (Bruker, 1996); cell SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: using SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536809018650/hb2962sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536809018650/hb2962Isup2.hkl
The complete reaction was carried out under nitrogen atmosphere and 195 K. t-BuLi (10 ml, 14 mmol) solution was added to 1,4-dibromonaphthalene (1 g, 3.5 mmol) solved in dry THF (12 ml) with continuous stirring. Meanwhile, red colour was observed because of LiBr formation. Later, to the resulting reaction mixture was added dropwise (CH3S)2 (1.24 ml, 14 mmol). After 1 h, the reaction was ended. Reaction mixture warming to room temperature was extracted with Et2O (3 × 25 ml). The extract was dried over Na2SO4 and concentrated. 1,4-Bis(methylthio)naphthalene as white needle-like crystals was obtained by crystallization from crude product solved in dichloromethane:hexan (1:19) system (708 mg, 92%), m.p. 369–371 K (lit. 370–371 K).
H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, and 0.9 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms.
Data collection: XSCANS (Bruker, 1996); cell SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: using SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./hb2962fig1thm.gif) | Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level. |
![[Figure 2]](./hb2962fig2thm.gif) | Fig. 2. View of the molecular packing diagram of compound (I) viewed down b axis. H atoms have been omitted for clarity. |
| C12H12S2 | F(000) = 464 |
| Mr = 220.34 | Dx = 1.327 Mg m−3 |
| Monoclinic, P21/c | Synchrotron radiation, λ = 0.75140 Å |
| Hall symbol: -P 2ybc | Cell parameters from 40396 reflections |
| a = 15.203 (3) Å | θ = 1.0–27.0° |
| b = 10.246 (2) Å | µ = 0.44 mm−1 |
| c = 7.1750 (14) Å | T = 153 K |
| β = 99.43 (3)° | Prism, colourless |
| V = 1102.6 (4) Å3 | 0.11 × 0.08 × 0.02 mm |
| Z = 4 |
| Bruker P4 diffractometer | 3013 independent reflections |
| Radiation source: sealed tube | 2619 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.019 |
| ω scans | θmax = 33.8°, θmin = 2.6° |
| Absorption correction: part of the model (ΔF) (XABS2; Parkin et al., 1995) | h = −20→20 |
| Tmin = 0.832, Tmax = 0.991 | k = −14→14 |
| 5197 measured reflections | l = −9→0 |
| 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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.109 | H-atom parameters constrained |
| S = 1.07 | w = 1/[Σ2(Fo2) + (0.0553P)2 + 0.1466P] where P = (Fo2 + 2Fc2)/3 |
| 3013 reflections | (Δ/σ)max = 0.001 |
| 127 parameters | Δρmax = 0.25 e Å−3 |
| 0 restraints | Δρmin = −0.25 e Å−3 |
| C12H12S2 | V = 1102.6 (4) Å3 |
| Mr = 220.34 | Z = 4 |
| Monoclinic, P21/c | Synchrotron radiation, λ = 0.75140 Å |
| a = 15.203 (3) Å | µ = 0.44 mm−1 |
| b = 10.246 (2) Å | T = 153 K |
| c = 7.1750 (14) Å | 0.11 × 0.08 × 0.02 mm |
| β = 99.43 (3)° |
| Bruker P4 diffractometer | 3013 independent reflections |
| Absorption correction: part of the refinement model (ΔF) (XABS2; Parkin et al., 1995) | 2619 reflections with I > 2σ(I) |
| Tmin = 0.832, Tmax = 0.991 | Rint = 0.019 |
| 5197 measured reflections |
| R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
| wR(F2) = 0.109 | H-atom parameters constrained |
| S = 1.07 | Δρmax = 0.25 e Å−3 |
| 3013 reflections | Δρmin = −0.25 e Å−3 |
| 127 parameters |
Experimental. Cubic fit to sin(theta)/lambda - 24 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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 | 0.90863 (2) | −0.04680 (4) | 0.76728 (6) | 0.0671 (2) | |
| S2 | 0.53023 (2) | −0.06992 (3) | 0.23860 (5) | 0.0558 (1) | |
| C1 | 0.85913 (9) | 0.07840 (13) | 0.3828 (2) | 0.0578 (4) | |
| C2 | 0.84525 (11) | 0.14096 (16) | 0.2131 (2) | 0.0700 (5) | |
| C3 | 0.76299 (11) | 0.13355 (17) | 0.0952 (2) | 0.0714 (5) | |
| C4 | 0.69472 (10) | 0.06351 (14) | 0.1496 (2) | 0.0592 (4) | |
| C5 | 0.70573 (8) | −0.00085 (11) | 0.32680 (17) | 0.0468 (3) | |
| C6 | 0.63478 (8) | −0.07293 (11) | 0.38797 (18) | 0.0469 (3) | |
| C7 | 0.65018 (9) | −0.13631 (14) | 0.55763 (19) | 0.0562 (4) | |
| C8 | 0.73388 (9) | −0.13004 (14) | 0.67599 (19) | 0.0585 (4) | |
| C9 | 0.80296 (8) | −0.05983 (12) | 0.62517 (19) | 0.0511 (4) | |
| C10 | 0.79008 (8) | 0.00626 (11) | 0.44685 (18) | 0.0478 (3) | |
| C11 | 0.90238 (12) | −0.15800 (18) | 0.9562 (3) | 0.0818 (6) | |
| C12 | 0.46292 (9) | −0.17829 (14) | 0.3515 (2) | 0.0625 (4) | |
| H1 | 0.91490 | 0.08300 | 0.45830 | 0.0690* | |
| H2 | 0.89120 | 0.18910 | 0.17560 | 0.0840* | |
| H3 | 0.75440 | 0.17620 | −0.02070 | 0.0860* | |
| H4 | 0.64030 | 0.05810 | 0.06910 | 0.0710* | |
| H7 | 0.60450 | −0.18460 | 0.59600 | 0.0670* | |
| H8 | 0.74230 | −0.17440 | 0.79060 | 0.0700* | |
| H11A | 0.95780 | −0.15720 | 1.04240 | 0.1230* | |
| H11B | 0.89100 | −0.24440 | 0.90620 | 0.1230* | |
| H11C | 0.85490 | −0.13220 | 1.02170 | 0.1230* | |
| H12A | 0.40410 | −0.18270 | 0.27870 | 0.0940* | |
| H12B | 0.45940 | −0.14650 | 0.47600 | 0.0940* | |
| H12C | 0.48920 | −0.26370 | 0.36040 | 0.0940* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0534 (2) | 0.0744 (3) | 0.0682 (3) | −0.0142 (2) | −0.0060 (2) | 0.0043 (2) |
| S2 | 0.0519 (2) | 0.0567 (2) | 0.0553 (2) | −0.0028 (1) | −0.0020 (1) | 0.0051 (1) |
| C1 | 0.0503 (7) | 0.0558 (7) | 0.0691 (8) | −0.0030 (5) | 0.0149 (6) | 0.0008 (6) |
| C2 | 0.0643 (8) | 0.0693 (9) | 0.0818 (10) | −0.0055 (7) | 0.0280 (7) | 0.0134 (7) |
| C3 | 0.0707 (9) | 0.0773 (10) | 0.0696 (9) | 0.0035 (7) | 0.0212 (7) | 0.0236 (8) |
| C4 | 0.0578 (7) | 0.0612 (7) | 0.0593 (8) | 0.0062 (5) | 0.0117 (6) | 0.0111 (6) |
| C5 | 0.0494 (6) | 0.0417 (5) | 0.0504 (6) | 0.0037 (4) | 0.0116 (4) | 0.0001 (4) |
| C6 | 0.0453 (6) | 0.0447 (5) | 0.0497 (6) | 0.0001 (4) | 0.0047 (4) | −0.0012 (4) |
| C7 | 0.0490 (6) | 0.0610 (7) | 0.0571 (7) | −0.0094 (5) | 0.0043 (5) | 0.0098 (6) |
| C8 | 0.0540 (7) | 0.0660 (8) | 0.0528 (7) | −0.0088 (6) | 0.0007 (5) | 0.0117 (6) |
| C9 | 0.0473 (6) | 0.0505 (6) | 0.0537 (7) | −0.0036 (5) | 0.0031 (5) | −0.0019 (5) |
| C10 | 0.0484 (6) | 0.0411 (5) | 0.0550 (6) | 0.0002 (4) | 0.0115 (5) | −0.0026 (5) |
| C11 | 0.0770 (10) | 0.0848 (11) | 0.0728 (10) | −0.0151 (9) | −0.0198 (8) | 0.0164 (8) |
| C12 | 0.0536 (7) | 0.0643 (8) | 0.0667 (8) | −0.0097 (6) | 0.0017 (6) | 0.0023 (6) |
| S1—C9 | 1.7611 (14) | C9—C10 | 1.4324 (18) |
| S1—C11 | 1.785 (2) | C1—H1 | 0.9300 |
| S2—C6 | 1.7657 (13) | C2—H2 | 0.9300 |
| S2—C12 | 1.7911 (15) | C3—H3 | 0.9300 |
| C1—C2 | 1.362 (2) | C4—H4 | 0.9300 |
| C1—C10 | 1.4204 (19) | C7—H7 | 0.9300 |
| C2—C3 | 1.392 (2) | C8—H8 | 0.9300 |
| C3—C4 | 1.370 (2) | C11—H11A | 0.9600 |
| C4—C5 | 1.4176 (19) | C11—H11B | 0.9600 |
| C5—C6 | 1.4341 (17) | C11—H11C | 0.9600 |
| C5—C10 | 1.4247 (18) | C12—H12A | 0.9600 |
| C6—C7 | 1.3656 (19) | C12—H12B | 0.9600 |
| C7—C8 | 1.411 (2) | C12—H12C | 0.9600 |
| C8—C9 | 1.3707 (19) | ||
| S2···S2i | 3.6864 (9) | ||
| C9—S1—C11 | 103.55 (8) | C1—C2—H2 | 120.00 |
| C6—S2—C12 | 103.82 (7) | C3—C2—H2 | 120.00 |
| C2—C1—C10 | 121.32 (14) | C2—C3—H3 | 120.00 |
| C1—C2—C3 | 120.65 (15) | C4—C3—H3 | 120.00 |
| C2—C3—C4 | 120.16 (14) | C3—C4—H4 | 120.00 |
| C3—C4—C5 | 121.03 (14) | C5—C4—H4 | 119.00 |
| C4—C5—C6 | 121.99 (12) | C6—C7—H7 | 119.00 |
| C4—C5—C10 | 118.74 (12) | C8—C7—H7 | 119.00 |
| C6—C5—C10 | 119.27 (11) | C7—C8—H8 | 119.00 |
| S2—C6—C5 | 116.91 (10) | C9—C8—H8 | 119.00 |
| S2—C6—C7 | 123.72 (10) | S1—C11—H11A | 109.00 |
| C5—C6—C7 | 119.34 (12) | S1—C11—H11B | 109.00 |
| C6—C7—C8 | 121.39 (13) | S1—C11—H11C | 109.00 |
| C7—C8—C9 | 121.24 (13) | H11A—C11—H11B | 110.00 |
| S1—C9—C8 | 123.49 (11) | H11A—C11—H11C | 109.00 |
| S1—C9—C10 | 117.36 (10) | H11B—C11—H11C | 109.00 |
| C8—C9—C10 | 119.15 (12) | S2—C12—H12A | 109.00 |
| C1—C10—C5 | 118.08 (12) | S2—C12—H12B | 109.00 |
| C1—C10—C9 | 122.34 (12) | S2—C12—H12C | 109.00 |
| C5—C10—C9 | 119.58 (11) | H12A—C12—H12B | 109.00 |
| C2—C1—H1 | 119.00 | H12A—C12—H12C | 109.00 |
| C10—C1—H1 | 119.00 | H12B—C12—H12C | 109.00 |
| C11—S1—C9—C8 | 7.08 (14) | C10—C5—C6—C7 | −1.81 (18) |
| C11—S1—C9—C10 | −172.38 (11) | C4—C5—C10—C1 | 0.28 (18) |
| C12—S2—C6—C5 | 175.91 (10) | C4—C5—C10—C9 | −179.02 (12) |
| C12—S2—C6—C7 | −5.94 (13) | C6—C5—C10—C1 | −179.94 (12) |
| C10—C1—C2—C3 | −1.4 (2) | C6—C5—C10—C9 | 0.76 (17) |
| C2—C1—C10—C5 | 1.0 (2) | S2—C6—C7—C8 | −176.70 (11) |
| C2—C1—C10—C9 | −179.70 (14) | C5—C6—C7—C8 | 1.4 (2) |
| C1—C2—C3—C4 | 0.4 (2) | C6—C7—C8—C9 | 0.1 (2) |
| C2—C3—C4—C5 | 0.9 (2) | C7—C8—C9—S1 | 179.38 (11) |
| C3—C4—C5—C6 | 178.97 (14) | C7—C8—C9—C10 | −1.2 (2) |
| C3—C4—C5—C10 | −1.3 (2) | S1—C9—C10—C1 | 0.93 (17) |
| C4—C5—C6—S2 | −3.80 (16) | S1—C9—C10—C5 | −179.80 (10) |
| C4—C5—C6—C7 | 177.96 (13) | C8—C9—C10—C1 | −178.56 (13) |
| C10—C5—C6—S2 | 176.43 (9) | C8—C9—C10—C5 | 0.71 (18) |
| Symmetry code: (i) −x+1, −y, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C1—H1···S1 | 0.93 | 2.60 | 3.0235 (16) | 108 |
| C4—H4···S2 | 0.93 | 2.58 | 3.0090 (17) | 108 |
Experimental details
| Crystal data | |
| Chemical formula | C12H12S2 |
| Mr | 220.34 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 153 |
| a, b, c (Å) | 15.203 (3), 10.246 (2), 7.1750 (14) |
| β (°) | 99.43 (3) |
| V (Å3) | 1102.6 (4) |
| Z | 4 |
| Radiation type | Synchrotron, λ = 0.75140 Å |
| µ (mm−1) | 0.44 |
| Crystal size (mm) | 0.11 × 0.08 × 0.02 |
| Data collection | |
| Diffractometer | Bruker P4 diffractometer |
| Absorption correction | Part of the refinement model (ΔF) (XABS2; Parkin et al., 1995) |
| Tmin, Tmax | 0.832, 0.991 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5197, 3013, 2619 |
| Rint | 0.019 |
| (sin θ/λ)max (Å−1) | 0.740 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.109, 1.07 |
| No. of reflections | 3013 |
| No. of parameters | 127 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.25, −0.25 |
Computer programs: XSCANS (Bruker, 1996), SCALEPACK (Otwinowski & Minor, 1997), DENZO (Otwinowski & Minor, 1997) and SCALEPACK (Otwinowski & Minor, 1997), using SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Acknowledgements
SGG gratefully acknowledges financial support from the MEC, projects MAT2006-01997 and Consolider Ingenio-2010, `Factoría Española de Cristalización', for the latter of which beam time provided by BM16 (ESRF) under proposal 16-01-706 is gratefully acknowledged.
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bondi, A. (1964). J. Phys. Chem. 68, 441–451. CrossRef CAS Web of Science Google Scholar
Bruker (1996). XSCANS. Bruker AXS Inc., Karlsruhe, Germany. Google Scholar
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Noreland, J., Olovsson, G. & Olovsson, I. (1992). Acta Cryst. C48, 1459–1462. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Noreland, J., Olovsson, G. & Olovsson, I. (1993). Acta Cryst. C49, 168–171. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Öncü, A., Büyükkıdan, N. S., Büyükkıdan, B. & Çakmak, O. (2006). Turk. J. Chem. 30, 235–241. 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
Parkin, S., Moezzi, B. & Hope, H. (1995). J. Appl. Cryst. 28, 53–56. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Underhill, A. E. (1992). J. Mater. Chem. 2, 1-11. CrossRef CAS Web of Science Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
| CRYSTALLOGRAPHIC COMMUNICATIONS |
Molecular electronics have attracted considerable attention because they are used for production electronic switches, memory cells or sensors. The most extensive range of the set compounds is based on planar organic donor molecules containing S or Se atoms (e.g. Underhill, 1992; Noreland et al., 1992; Noreland et al., 1993; Öncü et al., 2006. In this study, the synthesis and structure of the title compound, (I), are reported.
As shown in Fig. 1, the naphthalene group (C1–C10) of the title molecule (I) is essentially planar, with maximum deviations of -0.014 (1), -0.014 (1) and 0.018 (1) Å for C4, C8 and C6, respectively. Deviations from planarity in the title molecule which were calculated to the least-squares plane of the naphthalene group are: 0.014 (1) Å for S1, 0.112 (1) Å for S2, -0.221 (2) Å for C11 and -0.019 (1) Å for C12. The bond lengths and angles in (I) show normal values (Allen et al., 1987). The molecular packing of (I) as seen down the a axis is illustrated in Fig. 2. There is only one S···S contact near the van der Waals contact distance, 3.6 Å (Bondi, 1964): S2···S2i 3.6864 (9) Å [symmetry code: (i) -x + 1, -y, -z].