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access4-(Phenylsulfanyl)benzene-1,2-dicarbonitrile
aMarine College, Shandong University at Weihai, Weihai 264209, People's Republic of China, and bSchool of Chemistry & Chemical Technology, Shandong University, Jinan 250100, People's Republic of China
*Correspondence e-mail: mengfj@sdu.edu.cn, zhangxiaomei@sdu.edu.cn
In the title compound, C14H8N2S, the dicyano-substituted aromatic ring and the phenyl ring attached to the central S atom adopt an angular V-shaped configuration. The dihedral angle between the rings is 103.6°.
Related literature
The title compound is a precusor in the synthesis of phthalocyanine derivatives. For applications of phthalocyanines, see: Ao et al. (1995![[Ao. Q. (1995). Comput. Struct. 55, 119-126.]](../../../../../../logos/arrows/e_arr.gif "Ao. Q. (1995). Comput. Struct. 55, 119-126.")
); Rey et al. (1998); Zhang et al. (2009); Beltrán et al. (2004); LukCentyanets (1999); Shirk & Pong (2000).
![[Scheme 1]](pb2042scheme1.gif)
Experimental
Crystal data
|
Data collection: APEX2 (Bruker, 2004); cell SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810043011/pb2042sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810043011/pb2042Isup2.hkl
For general structure and background information on phthalocyanines, see: Zhang et al. (2009); For the synthesis, see: Rey et al. (1998).
Hydrogen atoms were placed in calculated positions and refined using a riding-model approximation with C—H = 0.93 Å, Uiso = 1.2Ueq (C) for aromatic H atoms and C—H = 0.96 Å, Uiso = 1.5Ueq (C) for methyl H atoms.
Dicyano compounds have been widely used to synthesize many useful materials such as phthalocyanines. Phthalocyanines are an interesting class of compounds, with increasingly diverse industrial and biomedical applications, for instance as dyes and pigments, materials for optical storage (Ao et al. 1995), liquid crystals, oxidation catalysts, solar cell functional materials, gas sensors, nonlinear optical limiting devices (Shirk et al. 2000), photodynamic therapy agents (LukCentyanets et al. 1999), antimycotic material, and corrosion inhibitors (Zhang et al. 2009). The title compound 4-phenylsulfanylphthalonitrile was prepared according to the method reported in the literature.
The dicyano substituted phenyl ring and the aromatic ring attached to the sulfur atom is planar and the angle involving C4—S1—C9 (103.590) clearly indicate the angular orientation of the phenyl rings with respect to the sulfur atom with in this compound.
The title compound is a precusor in the synthesis of phthalocyanine derivatives. For applications of phthalocyanines, see: Ao et al. (1995); Rey et al. (1998); Zhang et al. (2009); Beltrán et al. (2004); LukCentyanets (1999); Shirk & Pong (2000).
Data collection: APEX2 (Bruker, 2004); cell SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./pb2042fig1thm.gif) | Fig. 1. A view of (I) with the unique atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. |
| C14H8N2S | F(000) = 488 |
| Mr = 236.28 | Dx = 1.309 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2102 reflections |
| a = 7.8515 (7) Å | θ = 2.2–25.0° |
| b = 9.7739 (9) Å | µ = 0.25 mm−1 |
| c = 15.6248 (14) Å | T = 273 K |
| β = 91.544 (2)° | Block, colorless |
| V = 1198.61 (19) Å3 | 0.31 × 0.25 × 0.21 mm |
| Z = 4 |
| Bruker APEXII CCD diffractometer | 2102 independent reflections |
| Radiation source: fine-focus sealed tube | 1818 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.015 |
| phi and ω scans | θmax = 25.0°, θmin = 2.5° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −8→9 |
| Tmin = 0.928, Tmax = 0.950 | k = −11→11 |
| 5758 measured reflections | l = −14→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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.098 | H-atom parameters not refined |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.043P)2 + 0.3751P] where P = (Fo2 + 2Fc2)/3 |
| 2102 reflections | (Δ/σ)max < 0.001 |
| 154 parameters | Δρmax = 0.33 e Å−3 |
| 17 restraints | Δρmin = −0.38 e Å−3 |
| C14H8N2S | V = 1198.61 (19) Å3 |
| Mr = 236.28 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 7.8515 (7) Å | µ = 0.25 mm−1 |
| b = 9.7739 (9) Å | T = 273 K |
| c = 15.6248 (14) Å | 0.31 × 0.25 × 0.21 mm |
| β = 91.544 (2)° |
| Bruker APEXII CCD diffractometer | 2102 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1818 reflections with I > 2σ(I) |
| Tmin = 0.928, Tmax = 0.950 | Rint = 0.015 |
| 5758 measured reflections |
| R[F2 > 2σ(F2)] = 0.037 | 17 restraints |
| wR(F2) = 0.098 | H-atom parameters not refined |
| S = 1.04 | Δρmax = 0.33 e Å−3 |
| 2102 reflections | Δρmin = −0.38 e Å−3 |
| 154 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 | ||
| S1 | 1.02062 (6) | −0.13035 (5) | 0.20832 (4) | 0.0706 (2) | |
| N1 | 1.1713 (2) | 0.44401 (17) | −0.06030 (11) | 0.0689 (5) | |
| N2 | 1.5357 (2) | 0.1851 (2) | −0.00461 (12) | 0.0759 (5) | |
| C1 | 1.10678 (19) | 0.23614 (16) | 0.03502 (9) | 0.0428 (4) | |
| C2 | 1.23816 (19) | 0.14420 (16) | 0.05715 (10) | 0.0437 (4) | |
| C3 | 1.2075 (2) | 0.03475 (17) | 0.11030 (11) | 0.0496 (4) | |
| H3 | 1.2954 | −0.0253 | 0.1252 | 0.060* | |
| C4 | 1.0448 (2) | 0.01386 (16) | 0.14187 (11) | 0.0466 (4) | |
| C5 | 0.9148 (2) | 0.10349 (18) | 0.11842 (11) | 0.0508 (4) | |
| H5 | 0.8056 | 0.0890 | 0.1383 | 0.061* | |
| C6 | 0.9453 (2) | 0.21380 (17) | 0.06595 (11) | 0.0504 (4) | |
| H6 | 0.8571 | 0.2735 | 0.0512 | 0.061* | |
| C7 | 1.1412 (2) | 0.35200 (18) | −0.01832 (11) | 0.0498 (4) | |
| C8 | 1.4050 (2) | 0.16575 (18) | 0.02351 (12) | 0.0539 (4) | |
| C9 | 0.8157 (2) | −0.10711 (17) | 0.25164 (11) | 0.0493 (4) | |
| C10 | 0.7880 (3) | −0.0083 (2) | 0.31328 (12) | 0.0629 (5) | |
| H10 | 0.8762 | 0.0491 | 0.3316 | 0.075* | |
| C11 | 0.6272 (3) | 0.0044 (2) | 0.34748 (13) | 0.0723 (6) | |
| H11 | 0.6075 | 0.0708 | 0.3887 | 0.087* | |
| C12 | 0.4977 (3) | −0.0807 (2) | 0.32069 (14) | 0.0724 (6) | |
| H12 | 0.3900 | −0.0715 | 0.3434 | 0.087* | |
| C13 | 0.5263 (3) | −0.1780 (2) | 0.26123 (15) | 0.0736 (6) | |
| H13 | 0.4380 | −0.2358 | 0.2437 | 0.088* | |
| C14 | 0.6849 (2) | −0.1927 (2) | 0.22626 (12) | 0.0601 (5) | |
| H14 | 0.7032 | −0.2604 | 0.1857 | 0.072* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0552 (3) | 0.0589 (3) | 0.0988 (4) | 0.0124 (2) | 0.0230 (3) | 0.0307 (3) |
| N1 | 0.0704 (11) | 0.0639 (10) | 0.0736 (11) | 0.0084 (8) | 0.0214 (8) | 0.0192 (9) |
| N2 | 0.0501 (10) | 0.0816 (12) | 0.0971 (13) | 0.0050 (8) | 0.0241 (9) | 0.0081 (10) |
| C1 | 0.0433 (8) | 0.0425 (8) | 0.0428 (8) | 0.0005 (7) | 0.0046 (6) | −0.0009 (7) |
| C2 | 0.0387 (8) | 0.0459 (9) | 0.0470 (9) | 0.0015 (7) | 0.0079 (6) | −0.0033 (7) |
| C3 | 0.0418 (9) | 0.0483 (9) | 0.0590 (10) | 0.0091 (7) | 0.0062 (7) | 0.0042 (8) |
| C4 | 0.0442 (9) | 0.0439 (9) | 0.0520 (9) | 0.0004 (7) | 0.0064 (7) | 0.0012 (7) |
| C5 | 0.0373 (8) | 0.0530 (10) | 0.0623 (10) | 0.0005 (7) | 0.0082 (7) | 0.0071 (8) |
| C6 | 0.0397 (8) | 0.0517 (9) | 0.0600 (10) | 0.0069 (7) | 0.0039 (7) | 0.0072 (8) |
| C7 | 0.0458 (9) | 0.0522 (10) | 0.0519 (9) | 0.0062 (8) | 0.0100 (7) | 0.0016 (8) |
| C8 | 0.0449 (9) | 0.0535 (10) | 0.0638 (11) | 0.0065 (8) | 0.0098 (8) | 0.0049 (8) |
| C9 | 0.0517 (9) | 0.0456 (9) | 0.0510 (9) | 0.0027 (7) | 0.0070 (7) | 0.0115 (7) |
| C10 | 0.0732 (12) | 0.0524 (10) | 0.0626 (11) | −0.0007 (9) | −0.0059 (9) | 0.0000 (9) |
| C11 | 0.0989 (16) | 0.0647 (12) | 0.0539 (11) | 0.0253 (12) | 0.0141 (11) | −0.0029 (9) |
| C12 | 0.0647 (12) | 0.0775 (14) | 0.0762 (14) | 0.0134 (11) | 0.0239 (10) | 0.0126 (11) |
| C13 | 0.0578 (11) | 0.0763 (14) | 0.0875 (15) | −0.0109 (10) | 0.0137 (10) | −0.0022 (12) |
| C14 | 0.0647 (11) | 0.0573 (11) | 0.0588 (11) | −0.0039 (9) | 0.0129 (9) | −0.0059 (9) |
| S1—C4 | 1.7638 (16) | C5—H5 | 0.9300 |
| S1—C9 | 1.7770 (17) | C6—H6 | 0.9300 |
| N1—C7 | 1.142 (2) | C9—C14 | 1.375 (3) |
| N2—C8 | 1.143 (2) | C9—C10 | 1.385 (3) |
| C1—C6 | 1.386 (2) | C10—C11 | 1.389 (3) |
| C1—C2 | 1.404 (2) | C10—H10 | 0.9300 |
| C1—C7 | 1.436 (2) | C11—C12 | 1.370 (3) |
| C2—C3 | 1.379 (2) | C11—H11 | 0.9300 |
| C2—C8 | 1.440 (2) | C12—C13 | 1.353 (3) |
| C3—C4 | 1.397 (2) | C12—H12 | 0.9300 |
| C3—H3 | 0.9300 | C13—C14 | 1.381 (3) |
| C4—C5 | 1.387 (2) | C13—H13 | 0.9300 |
| C5—C6 | 1.379 (2) | C14—H14 | 0.9300 |
| C4—S1—C9 | 103.59 (7) | N2—C8—C2 | 178.3 (2) |
| C6—C1—C2 | 119.07 (14) | C14—C9—C10 | 119.68 (17) |
| C6—C1—C7 | 120.97 (14) | C14—C9—S1 | 119.29 (14) |
| C2—C1—C7 | 119.95 (14) | C10—C9—S1 | 120.97 (14) |
| C3—C2—C1 | 120.38 (14) | C9—C10—C11 | 119.38 (18) |
| C3—C2—C8 | 120.55 (14) | C9—C10—H10 | 120.3 |
| C1—C2—C8 | 119.07 (14) | C11—C10—H10 | 120.3 |
| C2—C3—C4 | 120.13 (14) | C12—C11—C10 | 120.21 (18) |
| C2—C3—H3 | 119.9 | C12—C11—H11 | 119.9 |
| C4—C3—H3 | 119.9 | C10—C11—H11 | 119.9 |
| C5—C4—C3 | 119.22 (15) | C13—C12—C11 | 120.05 (19) |
| C5—C4—S1 | 124.76 (12) | C13—C12—H12 | 120.0 |
| C3—C4—S1 | 116.01 (12) | C11—C12—H12 | 120.0 |
| C6—C5—C4 | 120.80 (15) | C12—C13—C14 | 120.9 (2) |
| C6—C5—H5 | 119.6 | C12—C13—H13 | 119.6 |
| C4—C5—H5 | 119.6 | C14—C13—H13 | 119.6 |
| C5—C6—C1 | 120.39 (15) | C9—C14—C13 | 119.80 (18) |
| C5—C6—H6 | 119.8 | C9—C14—H14 | 120.1 |
| C1—C6—H6 | 119.8 | C13—C14—H14 | 120.1 |
| N1—C7—C1 | 178.87 (19) |
Experimental details
| Crystal data | |
| Chemical formula | C14H8N2S |
| Mr | 236.28 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 273 |
| a, b, c (Å) | 7.8515 (7), 9.7739 (9), 15.6248 (14) |
| β (°) | 91.544 (2) |
| V (Å3) | 1198.61 (19) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.25 |
| Crystal size (mm) | 0.31 × 0.25 × 0.21 |
| Data collection | |
| Diffractometer | Bruker APEXII CCD |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
| Tmin, Tmax | 0.928, 0.950 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5758, 2102, 1818 |
| Rint | 0.015 |
| (sin θ/λ)max (Å−1) | 0.595 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.098, 1.04 |
| No. of reflections | 2102 |
| No. of parameters | 154 |
| No. of restraints | 17 |
| H-atom treatment | H-atom parameters not refined |
| Δρmax, Δρmin (e Å−3) | 0.33, −0.38 |
Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This work was supported by the Postdoctoral Scientific Foundation of China (grant No. 20070411093), the Postdoctoral Scientific Foundation of Shandong Province (grant No. 200603070) and Independent Innovation Foundation of Shandong University, IIFSDU.
References
Ao. Q. (1995). Comput. Struct. 55, 119–126. Google Scholar
Beltrán, H. I., Esquive, R., Sosa-Sánchez, A., Sosa-Sánchez, J. L., Höpfl, H., Barba, V., Farfán, N., Galicia García, M., Olivares-Xometl, O. & Zamudio-Rivera, L. S. (2004). Inorg. Chem. 43, 3555–35557. Web of Science PubMed Google Scholar
Bruker (2001). SAINT-Plus. Bruker AXS Inc., Madison,Wisconsin, USA. Google Scholar
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LukCentyanets, E. A. (1999). J. Porphyrins Phthalocyanines, 3, 424–432. Google Scholar
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Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany. Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Dicyano compounds have been widely used to synthesize many useful materials such as phthalocyanines. Phthalocyanines are an interesting class of compounds, with increasingly diverse industrial and biomedical applications, for instance as dyes and pigments, materials for optical storage (Ao et al. 1995), liquid crystals, oxidation catalysts, solar cell functional materials, gas sensors, nonlinear optical limiting devices (Shirk et al. 2000), photodynamic therapy agents (LukCentyanets et al. 1999), antimycotic material, and corrosion inhibitors (Zhang et al. 2009). The title compound 4-phenylsulfanylphthalonitrile was prepared according to the method reported in the literature.
The dicyano substituted phenyl ring and the aromatic ring attached to the sulfur atom is planar and the angle involving C4—S1—C9 (103.590) clearly indicate the angular orientation of the phenyl rings with respect to the sulfur atom with in this compound.